Inorganic chemistry
Ionic Compound
Three Dimensional arrays of charged particles.
Non- Planar H2O2
C2
What is the point group of OC(CH3)2?
C2V
Planar trans-H2O2
C2h
NH3
C3v
PF3
C3v
PH3
C3v
BrF5
C4v
When have multiple chelate rings that are not coplanar, need way to describe their relative positions. 3 [chelate] ring structures like [Co(en)3]+3 can be treated like bladed propellers. The CCW (LH) and CW (RH) characters are labeled how?
CCW is λ (Lambda) CW is Δ remember L for Lambda is like left
Coordination number(CN)
CN of a sphere in a close-packed arrangement(the Number of Nearest Neighbors) is 12
What ligands make delta o large?
CN- > bipy > en/NH3
cyanide (-CN) binds better to Fe+2 or Fe+3? why?
CN- can bind both, but binds better to Fe+3! Fe+3 more electron deficient
We established that reduction of Fe+3 less likely to happen with CN- as ligand (than with h2o). What effect is CN- having? (stabilizing Fe+2 or Fe+3?) Is this consistent with what we know about cyanide as good π acceptor?
CN- makes reduction of Fe+3 less likely...bc E° = +0.36 is lower...so CN- is kinda stabilizing the Fe+3...happy as it is this contradicts what is expected from π acceptor like CN- bc should be happier bonding to electron rich Fe+2 ...in this case, π accepting ability of CN- less important. Perhaps electrostatics more dominant (CN- is neg and wants to be with more + Fe+3)
What ligands make delta o small?
Cl- < H2O < NH3/en
what is the central metal in the vitamin B12 complex
Co(III)
Inert
Conjugate of a strong acid or base - Almost completely unreactive
Geometric Isomerism
Geometrically different molecules when 3D Trans- Cis
Molecular Formula
Gives the exact number of atoms of each element in the compound and gives the exact number of atoms of each element in the compound.
Photosynthesis Equation
Glucose: 180 g/mol Water: 18 g/mol CO2: 46 g/mol
Molar Mass
Grams per mol (g/mol)
Draw and explain an energy level diagram for HF
H's 1s electron interacts with F's 2p electrons. 2s electrons are too low in energy to interact with 1s electrons F's orbitals are much lower in energy than H because it is the more electronegative atom The 2s electrons are in non-bonding orbitals The 2px and 2py are also in non-bonding orbitals because the orbitals do not align with the s orbital for a sigma bond to form (positive and negative overlaps) There is one sigma s orbital and an antibonding sigma s orbital however only the sigma s orbital has electrons in it
examples of neutral ligands? (4)
H2O (oxygen has unpaired e's on it), amines (:NR3), phosphines (:PR3), carbonyl (:C=O:)
Heisenberg uncertainty principle
It is impossible to simultaneously determine, with perfect accuracy, the momentum and the position of an electron
Spinel Structure
MgAl2O4, ZnFe2O4 AB2C4 (A) Cations occupy 1/8 of Tetrahedral holes (B) cations occupy half of the Octohedral holes (CCP)
What is lattice energy?
∆U of an ionic compound is the change in internal energy that accompanies the formation of one mole of the solid from its constituent gas-phase ions at 0K.
Inorganic Materials as Excipients
• Excipients are components of a finished drug product other than the API.
What are Antacids
• Substance that neutralizes stomach acidity • This is done by directly neutralizing the acid or block the secretion of acid by gastric cells to reduce the acidity
acetate is monodentate or bidentate? how named?
•can be either (monodentate = kappa1, bidentate = k2) •has negatively charged oxygen (O-) which can be act as good lewis base •also has 2nd neutral oxygen (=O) which can act as another binding site
Δo (crystal-field splitting parameter) is a value used to quantify the energy difference btw octahedral d orbitals. The average of all 5 d orbitals in coord complex is higher evergy lvl than than free metal ion, but dz2, dx2-y2 are higher than others as explained already. What is exact energy difference in terms of Δo?
•dz2, dx2-y2 (Eg) are 0.6Δo above the average total energy of +0.6Δo x 2 = +1.2Δo •dxy, dxz, and dyz (Tg) are 0.4Δo below total energy of -0.4Δo x 3 = -1.2Δo
How do incoming ligands affect d orbitals? What happens to energy levels?
•in free (unbound) metal atom, d orbitals all same energy level (degenerate) •when ligands (as lewis base) donate electrons to d orbitals, energy lvl goes up bc more repulsion •amount energy ↑ depends on type of d orbital involved in interaction
For octahedral complexes that have 3 of the same ligand e.g. for 'a' in Ma3b2c1, can be arranged in meridonal or facial geometry. What does this mean?
•meridonal (mer) when the 3 identical ligands are on same plane (see pic) •facial (fac) when are not on one plane...facial form triangular face of octahedron if connect dots btw them the 3 pts
How does Δt compare to Δo?
•splitting pattern flipped around with e is lower than t2 •also split (now called Δt) is smaller for tetrahedral symmetry (~0.5Δt) ...so probably tend to be high spin
How does Δt (crystal-field splitting parameter) btw Td d orbitals compare with Δoct? How will MO diagram be arranged (for d orbitals)?
•splitting pattern flipped around with e is lower than t2 •also split (now called Δt) is smaller for tetrahedral symmetry (~0.5Δt) •nature of the overlap of charges/orbitals for the tetrahedral and octahedral are different ~pic shows MO diagrams..most important to know for exam is Oh has triplet (T2g) on bottom and for Td it's on top..to remember T is wider at top!
In the form of a complex, the metal center acts as a Lewis __________ by __________ electrons, and the ligand acts as a Lewis __________ by ___________ electrons.
acid; accepting base; donating
Hard bases are characterized by
a very high electronegativity and relatively small size
lead acid battery
a) Pb anode and PbO2 cathode b) electrodes are coated with lead sulfate.
When going from d⁸ to d⁹, does the electron go into the dx²-y² or the dz² orbital
a) if the electron goes into the dx2-y2 it wll interact with 4 ligands, the electron will repel x and y axes ligands increases M-L bond length b) if the electron goes into the dz2 it interacts with 2 ligands, the extra electron will repel z axis ligands, increasing M-L bond length
weiss indices
a,b,c of the cube
Draw acac
acetylacetone but the resonance has partial bonds between the two O atoms with the C in the middle with a negative charge
What d orbital has highest energy for square planar complex?
dx2-y2
For electrons to be unpaired, repulsion energy must be
greater than difference in energy between orbitals (pairing energy)
The larger the value of the formation constant the
greater the thermodynamic stability of the new complex
Molecule
group of atoms bonded together so 2 oxygen atoms that bond form O2
Draw the lewis structure for [S2CO]2- (C is central)
http://mmrc.caltech.edu/chem1a/Wk%205%20Lewis%20VSEPR/Lewis%20Dot%20Structures.pdf Question 4
Let's say have 2 chelate rings. Think of example why might not be appropriate to name λ or Δ?
if rings are in the same plane
symmetry and bonding
if symmetry does not match it leads to nonbonding interactions
In a period from left to right as the charge on ion ___________, lattice ___________.
increases , increases
Crystal field theory is the __________ model
ionic
Hard acids and bases tend to be highly charges and non-polarizable, therefore their main interaction is
ionic
What does the symmetry symbol σv mean?
mirror plane is in line with the axis of rotation
What does the symmetry symbol σh mean?
mirror plane is perpendicular to the axis of rotation
ligands can be subdivided into what 2 categories? (oversimplification)
neutral ligands negatively charged ligands
Octohedral d⁸ to d¹⁰ are all single state configurations and therefore have:
no low spin
Can tetrahedral molecules be classified as cis or trans?
nope
Atomic number
number of protons or electrons in an atom's nucleus; ie Oxygen=8; number of protons is primary characteristic that distinguishes atoms from each other.
miller indices
number replacing a, b, and c
Ionization Isomerism
occurs when a ligand and a counterion in one compound exchange places. (SOLUBLE IN WATER) [PtBr2(NH3)4]Cl2 [PtCl2(NH3)4]Br2 Br and Cl switch from in complex to out
Complexes of Cr(III) and Co(III) are always what geometry?
octahedral
The symmetry labels, t2g (dxy, dxz, dyz) and eg (dx²-y², dz²) apply to __________ geometry
octahedral
Complexes with a coordination number of 6 are
octhedral (d²sp³ hybridised)
Optically Active
one enantiomer rotates the plane of polarized light in one direction and the other rotates at equal angle in opposite direction. NO TRANS
A molecule cannot be _______ if it has a center of Inversion
polar
lattice energy is always be_______, since this will always be an ______________
positive, endothermic reaction.
K₂[Mn(H₂O)₆](SO₄)₂
potassium hexaaquamanganese(II) sulfate
try to do MO diagram for generic Td molecule with 5 electrons in metal d orbital (use character table!)
t2* -↑-↑-↑ e (nonbonding) -↑-↑ ...t2* & e will be above bonding orbitals t2 and a1
Light of frequency V is absorbed. In the excitation of a metal, the electron moves rom the _________ orbital to the __________ orbital
t2g → eg
Which geometry has longer M-L bonds in the z axis
tetragonal
The symmetry labels, t2g (dx²-y², dz²) and eg (dxy, dxz, dyz) apply to __________ geometry
tetrahedral
Complexes with a coordination number of 4 are
tetrahedral (sp³ or sd³ hybridised) square planar (dsp² hybridised)
Polymorphism
the ability to adopt different crystal forms under different conditions of pressure and temp
Lattice energy mainly depends upon__________ and__________in a crystal lattice.
the charge of ions & inter ionic distance
Coordination Number
the number of ions of opposite charge that surround the ion in a crystal
Conjugate Base
when an acid loses a proton
what is a interchange mechanism
when bonding and cleaving is concurrent and no detectable intermediate canm be found
{important} Again what makes a weak field ligand (Δo small)?
when have both sigma donor and pi donor interactions in Oh complex!! remember that t2g becomes a antibonding MO when have π donor (nonbonding if only σ donors (Ag, Eg, T1u) on ligand)
right handed propeller is like right handed screw meaning ?
when turn propeller clockwise, moves away from observer when turn RH screw CW, screw goes into wood
So established that high spin less πc, but have to jump Δo. When is high spin more likely to be favored over has low spin?
when Δo is small e.g. in weak field ligand, it's easier to make jump into eg* lvl = high spin large Δo (strong field ligands) tends to favor favor low spin..can't jump that high
amino acids can be used as ligands to bind to metal ions, the amino acid side chain acts as
a lewis base
complex compound
a metal surrounded by ligands
Deuterium and its compounds are used as________
a non-radioactive label in chemical experiments and in solvents for 1H-NMR spectroscopy.
In their elemental oxidised state, transition metals have
a partially filled d shell, ie. they display magnetic properties
Ligands exert __________, not a spherical field
a point charge
Speed of Light
c= 3 * 10^8 m/s
Hydrogen_____
can combine chemically with almost every other element and forms more compounds than does any other element.
Optical isomers occur when a species
can not be superimposed
electron configuration
capacity of 2 electrons in 1st shell capacity of 8 in 2nd shell capacity of 18 in 3rd shell
what is the name of the therapy used to treat lead poisoning
chelation therapy, using EDTA (N2O4 donor)
ligands that more than one binding site to metal center = ?
chelators ...ability to hold metal atom like a claw (name from Greek 'chill' meaning claw)
Coordination compounds can often be arranged in as many different stereoisomers. For the following stereoisomer (pic on answer), which is cis and which is trans?
cis on left trans on right
what is the primary difference between cisplatin and the second generation compound carboplatin?
cisplatin must be delivered IV whilst carboplatin can be administered orally
Faraday
- 96,485 C/mol e- ; amount of charge contained in one mole of electrons - For the MCAT: 10^5 C/ mol e- - Gas and deposition of elements on electrodes is directly proportional to the number of electrons being transferred during the oxidation reduction reaction.
Coupling Reactions
- A common method for supplying energy for non spontaneous reactions is by coupling non spontaneous reactions to spontaneous - Combustion of glucose is exergenic; the formation of peptide bonds is endergenic. - Energy from the combustion can be stored in the peptide bonds in GTP, which are then lysed to provide the energy for forming peptide bonds.
Graham's Law of Effusion
- A gas with a higher molar mass will leak more slowly than a gas with a lower molar mass. - Ex) Both neon and oxygen will leak at a slower rate than helium.
Electronegativity
- A measure of the attractive force that an atom will exert on an electron in a chemical bond.
Combustion Reaction
- A special type of reaction that involves a fuel, usually a hydrocarbon and an oxidant ( normally oxygen). - Products are usually water and carbon dioxide
Electrodes in a chemical cell
- AN OX and a RED CAT - Anode (-) is the site for oxidation; reduction occurs at the cathode (+).
Bronsted Lowry Base
- Accepts H+ - Not limited to aqueous solutions like Arrhenius - OH-, NH3, and F- are all bases due to their ability to accept a hydrogen ion; however, neither NH3 or F- can qualify as Arrhenius base because they can't dissociate to produce an excess of OH- ions in aqueous solutions.
Acid Base Nomenclature
- Acid from anions that end in ide get the prefix hydro and the ending -ic - if the anions end in -ite ( less oxygen) then the acid will end in -ous acid - If the anions end in ate ( more oxygen) then it will end with ic
Anions and cations
- Anions are attracted to the anode - Cations are attracted to the cathode.
Reaction Quotient
- At any point in time during a reaction, we can measure the concentrations of all of the reactants and products and calculate the reaction. - Qc < Keq ; Delta G < 0; forward reaction - Qc > Keq; Delta G forward > 0; reverse reaction - Qc = Keq; Delta G = 0; dynamic equilibrium - Kc >> 1 the equilibrium mixture will favor products over reactants.
Lewis Acid
- Electron Acceptor - Electrophile
Lewis Base
- Electron Donor - Nucleophile
Quantum Mechanical Model
- Electrons do not travel in defined orbits, but rather localized in orbitals - Orbitals: A region of space around the nucleus defined by the probability of finding an electron in that region of space.
n + l rule
- Electrons fill the principal energy levels and subshells according to increasing energy level.
Effective Nuclear Charge (Zeff)
- Electrostatic attraction between the valence shell electrons and the nucleus. - a measure of the net positive charge experienced by the outermost electrons. - Zeff increases from left to right - The values of q1 and q2 can represent the net charge of the nucleus and valence electron shell, respectively.
Quantum
- Energy difference between energy levels. First described by Planck. - Electrons can only exist at certain energy levels. - The energy of an electron increases the further it is from the nucleus.
Electron Affinity
- Energy dissipated by a gaseous species when it gains an electron. - If a reaction is exothermic then the electron affinity is positive.
First Law of Thermodynamics
- Energy is never created nor destroyed; simply changes from one form to another. - Delta U: change in internal energy of the system - Q: heat added to the system - W: Work done on the system
Second Law of Thermodynamics
- Energy spontaneously disperses from being localized to becoming spread out. - Q is heat that is lost or gained - T is temperature in Kelvin - units: J/ (mol * K)
Gibbs Free Energy
- Faraday constant is expressed in coulombs (J/V); therefore, Delta G must be expressed in J not KJ - Similar to W = q*Delta V ; q across a potential difference Delta V: n * F - Delta G and E cell value always have an opposite sign.
Atomic Absorption Spectrum
- For each element is unique - For an element to jump from a lower energy to a higher one, it must absorb an amount of energy precisely equal to the energy difference between the two levels.
Reduction
- Gain of electrons - e+ is on the reactant side
Empirical Formula
- Gives the simplest whole number ratio of the elements in the compound. - CH_2O indicative of monosaccharide include glucose, fructose, and galactose.
Main Group
1A: hydrogen and alkali metals which lose e- easily 4A (#14): Carbon 5A (15): Nitrogen 6A (16): Oxygen 7A (17): Halogen (F, Cl, Br, I) 8A (18): noble or inert gases
Bidentate ligands bind to a metal center via how many donor atoms?
2
Electronegative Elements increase Acidity
As Cl- gets closer to the acidic hydrogen, PKa gets lower Ex) figure 10.6
Answer: Look at triangular face from 2°clock point of view so 3 ligand towards u and 3 away from in 69 position (inverted peace signs)..then reconnect bridges to original atoms (edge of propellers.
As can see in pic, have λ (λλλ) Tricky is knowing what view to take..how to orient original structure to make it look like propeller.
Ionic Crystals (define and example)
Brittle, poor conductor, high melting point. Example: NaCl, Caco3, MgO
What group is number 18?
Noble gases
what is the name of [PtCl2(en)2]Cl2
dichlorobis(ethylenediamine)platinum(IV) chloride
the preference of ligands towards their own HSAB type is refered to as
symbiosis
Review Hund's Rule regarding πc vs πe.
"empty bus rule" electron fill empty orbitals first..before pairing...in order to maximize multiplicity (# of unpaired electrons plus 1) and minimize coulombic πc (electrostatic repulsion) also requires that electrons be placed to give max number of parallel spins, which ↑πe (exchange energy) and lowers energy of orbitals (more stable)
Atomic Mass/Mass Number
# of protons + neutrons; Hydrogen has 1 proton, 0 neutrons, mass number =1; Oxygen has 8 protons and 8 neutrons, mass number = 16.
dien = ? (just look at answer) ?_dentate?
'dien' is abbreviation for dienthlenetriamine it is tridentate
How do you account for single and double bonds when counting the valence electrons of a central atom when working out the shape of a molecule?
(+1 for every single bond) -1 for a double, -2 for a triple
Name a few examples of inorganic elements (transition metals etc) in industry. (just look at answer)
(1) magnetic resonance (Gd, Mn in metal responsive MRI), (2)chelation, (3)redox with Fe, Cu to induce degradation of protein, (4)acid-base catalysis blas blas
Name a few examples of inorganic elements (transition metals etc) in biological systems. (just look at answer)
(1)atom transfer e.g. Fe heme grp binding to O2, (2)electron transfer (cytochromes, vitamins e.g. cobalamine), Na/K channels, (3)protein structure e.g. Zn finger (4)nucleic acid structure e.g. Mg stabilization of tRNA (5)acid-base catalysis, (6)signalling (Ca+, NO), etc
How do you find the bond order?
(No. of antibonding MO - No. of bonding MO)/2
Body Center cubic structure
(bcc) Coordination Number 8
sigma bonding and antibonding symmetry
* symmetric to rotation along the z axis.
law of rationality of indices
*for any crystal a set of 3 coordinates can be so chosen that all faces of the crystals will either intersect these axes or be parallel to some of these axes.
unit cell
*limited number of atoms *applies to crystalline solids only. *smallest repeating unit of a structure which carries all the info necessary to construct unambiguously an infinite lattice.
Trigonal Pyramidal
- 2 lone pairs - ClF3
Standard Conditions
- 25 C or 298 K - 1 atm - 1 M concentration - used for kinetics, equilibrium, thermodynamics problem, electrochemical cell voltage
Definition of Rate
- 2A + B -> C - Negative sign in front of the rate expression for the reactants - Expressed in moles per liter per sec (mol/ L *s) or molarity per sec (M/ s)
Maximum number of electrons within a subshell
- 4l+2 - s = 2; p = 6; d = 10 ; f = 14
Charle's Law
- At constant pressure, the volume of a gas is proportional to its absolute temperature - V1/T1 = V2/T2
Solvation
- Breaking intermolecular forces between solubles and forming intermolecular forces between solubles and solvents - Water is a solvent
Neutralization Reaction
- Ca(OH)2 + H2SO4 -> CaSO4 +H2O - Acid & base = Salt and water
Keq Rules
- Characteristic of a particular reaction at a given temp; the equilibrium constant is temperature dependent. - The larger the Keq, the farther to the right the equilibrium position - if the equilibrium constant for a reaction written in one direction is Keq, the equilibrium constant for the reverse reaction is 1/ Keq .
Triple point
- Combination of pressure and temperature at which 3 phases are at equilibrium
Square Planar
- Consists of 4 Atoms and 2 pairs of electrons, one above and one below.
Electromotive Force (emf or Ecell)
- Corresponds to the voltage or electrical potential difference of the cell. - Positive, the cell is able to release energy (Delta G<0), spontaneous - Negative, the cell is to absorb energy (Delta G > 0), nonspontaneous. - Free energy change and electromotive force always have opposite signs. - Movement of electrons is from anode to cathode, and the current (I) runs from cathode to anode
Concentration Cells
- Current is generated as a function of a concentration gradient established between the two solutions surrounding the electrodes. - Voltage is zero if the concentration is equal. - Voltage of the concentration can be calculated using the Nernst equation.
The reversible reaction
- Delta H > 0; Endothermic; Heat act as a reactant - Delta H < 0; Exothermic, Heat act as a product - Always toward whichever side has the lowest total number of moles of gas.
Enthalpy
- Delta H > 0; Endothermic; Heat act as a reactant - Delta H < 0; Exothermic, Heat act as a product - Delta H = heat (Q) under constant pressure.
Quantum Numbers
- Describe any electron in an atom - Principal Quantum number, n: average energy of a shell. - Azimuthal quantum number, l: describes sub shells within a given principal energy level (s, p, d, f) - Magnetic Quantum number, ml: Specifies the particular orbital within a subshell where an electron is likely to be found. - Spin Quantum number, ms: indicates the spin orientation (+/- 1/2)
State Functions
- Describe the system in an equilibrium state - Pressure, density, temperature, volume, enthalpy, internal energy, Gibbs free energy, entropy.
Real Gases
- Deviate from ideal behavior under high pressure ( low volume) and low temperature conditions.
First order Reaction
- Directly proportional to only one reactant - k has units of s^-1 - Rate doubles as concentration doubles - ex) reactive decay - Concentration vs. Time results in a non-linear graph - Formation of product is dependent on the concentration of the reactant. - slope of ln [A] vs. time is -k
Average Kinetic Energy
- Directly proportional to the temperature of a gas in kelvins. - Molecules are elastic and thus do not result in loss of energy. - AVG kinetic energy of any gas as a whole is the same at a given temperature
Arrhenius Acid
- Dissociate to form an excess H+ in solution. - Contain H at the beginning of their formula (HCL, HNO3, H2SO4) - limited to aqueous solutions - Since water does not produce an excess of H+ in solutions, can't be an acid like BLA
Arrhenius Base
- Dissociate to form an excess of OH- in solution - Contains OH at the end of their formula (NaOH, Ca(OH)2, Fe(OH)3, and so on.)
Rate Law
- Does Not depend on the concentration of products - The exponents are unrelated to stoichiometric coefficients, so the amount of A consumed is not equal to the amount of B consumed.
Bronsted - Lowry Acid
- Donates H+ ions - Not limited to aqueous solutions like Arrhenius - H2O is able to donate a proton to other species
Energy of the electron
- E is the energy of the electron - RH: Rydberg unit of energy; 2.18*10^-18 J/electron - n: Principal quantum number - Due to the negative sign, (E) is directly proportional to the principal quantum number (n) - Positive E: Emission of energy (electrons move to orbits of lower energy) - Negative E: Absorption (color we see is the light that is not absorbed by the compound) - Part of Bohr Model
Nernst Equation
- Ecell is the emf under standard conditions - R is the ideal gas constant .0831 (numerator) - F is the Faraday constant 10^5 C / mol e in the denominator - Q is reaction quotient - T = 298 K (numerator) - Simplified version that brings out R, T and F is E cell - .0592/n log Q
Alkali Metals
- Group 1A; active metals because they are so reactive and are not naturally found in their neutral state. - Densities are lower than other metals - Zeff values are very low which means low ionization energy, low electron affinity, and low electronegativity - React violently with water; therefore, forming strong bases.
Alkaline Earth Metals
- Group 2; active metals because they are so reactive and are not naturally found in their neutral state. - slightly higher nuclear charges, but though smaller atomic radii.
Ions that form salt that are always soluble
- Group I metals - Ammonium (NH4), Nitrate (NO3), Acetate (CH3COO)
Chalcogens
- Group VIA or 16; Oxygen and sulfur - Heavier ones are toxic but lighter ones are non toxic. - small atomic radii & large ionic radii
Halogens
- Group VIIA or Group 17 - Highly reactive non metals; desperate to complete their valence electrons. - Mostly found in diatomic molecules. - Gaseous ( F2 & Cl2); Solid (Br2); Liquid (I2)
Heat Transfer Equation
- Heat transfer ( no phase change) - Heat capacities: mass times specific heat ( m*c) - sweating cools you down by giving energy to the sweat to make it evaporate - Specific heat of water ( in calories) = 1 cal/ g*k
Latent Heat
- Heat transfer used during phase changes - Enthalpy of an isothermal process - units cal/g
Carbonate reacts in water to form:
- Hydroxide (OH) is produced. - Red litmus paper would turn blue in a basic solution. - CO_3 and H_2O -> HCO_3 and OH-
Catalyst
- Inc. reaction rate without being consumed in the reaction. - Dec. in the energies of the activation energy, for both forward and reverse rxn. - no impact on equilibrium position, Keq..... they will not transform a non spontaneous reaction to spontaneous.
Ideal Gas
- Individual volume and intermolecular forces are negligible - No volume or intermolecular forces between molecules in an ideal gas environment
Ebulliator
- Introduce small air bubbles in the system; same function provided by a boiling chip at atmospheric pressure. - The air bubbles break the surface tension of the liquid being heated and prevent superheating and bumping.
Sparingly Soluble Salts
- Ionic compounds that have a very low solubility in aqueous solutions. - Ex) Silver Chloride (AgCl) -
Solubility Product Constant (Ksp)
- Ksp is just a speciaized form of Keq, so use the same concept as you do for all equilibrium, including Le Chatelier's. - Temperature and Pressure dependent - Generally increases with increasing temp for non gas solutes and decreases for gas solutes. - Lower Ksp forms a precipitate
Water Dissociation Constant
- Kw - Higher Temperature above 298 K = Higher Kw = Endothermic nature of the autionization reaction - Will change if the temperature changes, will impact the pH
Intermolecular Forces
- Larger intermolecular forces correspond to higher boiling points. - London Dispersion: nobel gas with a full octet; it's why they can liquefy. - Dipole- Dipole interactions: polar molecules such as Acetone and Isopropyl alcohol ( it can also form hydrogen bonds) - Ionic Bonds : such as KCl
Amphoteric
- Like an acid in a basic environment or vice versa - Ex) water, HSO4-, Hydroxide of certain metals ( Al, Zn, Pb, and Cr) - ex) Amino Acids intermediate with both cationic and anionic character = zwitterion intermediate - Acid : release a proton
Kinetic and Thermodynamic Control
- Lower temperature: Kinetic Product; Forms faster - Higher temperature: Thermodynamic Product; free energy is much lower; greater stability; more negative Delta G
Paramagnetic Materials
- Materials have Unpaired electrons that align with magnetic fields, attracting material to a magnet.
Diamagetic Materials
- Materials have all paired electrons, which cannot easily be realigned; they are repelled by magnets.
Sphygmomanometer
- Medical device that measure blood pressure - unit of measurement is mmHg - Normal : 120 mmHg systolic and 80 mmHg diastolic (120/80) - Hypertension: > 140 mmHg systolic or > 90 mmHg diastolic - Systolic: Heart Contraction - Diastolic: Heart relaxation
Making a material nanoscale can change its
- Melting temperature • Magnetization • Ability to hold charge • Structure • Chemical reactivity
Nobel Gases
- Minimal chemical reactivity - High Ionization energy - Extremely low boiling point & exist as gases at room temperature. - Virtually nonexistent electron negativities and electron affinities.
Activation Energy
- Minimum energy needed for chemical reaction to occur.
Transition State
- Molecules collide with energy equal to or greater than the activation energy - Has greater energy than both the reactant and the product
Isobaric
- No change in pressure, line appears flat in a P-V graph
Isothermal
- No change in temperature; Delta U = 0, Q = W - Temperature and the internal energy of the system is constant throughout. - Hyperbolic curve on a pressure-volume graph (P-V graph) - Work is represented by the area under the graph, but also the heat that entered the system. -
Isovolumetric / isochoric
- No change in volume - W = 0, Delta U = Q
Adiabatic
- No heat exchange; Q = 0, Delta U = -W
Electrolytic Cells
- Nonspontaneous; require the input of energy; electrolysis - Gibbs free energy is positive and electromotive force is negative (emf)
Atomic Number
- Number of Protons - Number of Protons = Number of Electrons (in a neutral atom)
Zeroth Law of Thermodynamics
- Objects are in thermal equilibrium only when their temperatures are equal
Second order Reaction
- Proportional to either the concentration of two reactants or to the square of the concentration of a single reactant. - k has units of M^-1s^-1 - Concentration vs. Time results in a non-linear graph - Formation of product is dependent on the concentration of the reactant. - slope of 1/ [A] vs. time is k
Atomic Mass Number
- Protons + Neutrons - Electrons are not included in mass calculations because they are much smaller. (1/2000) that of a proton.
Transitional Metals
- They take on multiple oxidation states, which explains their ability to form colorful complexes with nonmetals in solution and their utility in certain biological systems.
Enzymes that catalyze oxidation reduction reaction
- Pyruvate dehydrogenase complex - Succinate dehydrogenase complex - When pyruvate cannot be oxidized to acetyl- CoA, it is fermented to lactic acid - Iron in hemoglobin undergoes rounds of oxidation and reduction as it carries oxygen from the lungs to tissues.
Planck Relation
- Quanta: Energy emitted as electromagnetic radiation from matter comes in discrete bundles. - E = hf - h= 6.626*10^-34 J*s - Energy is inversely proportional to wavelength
Arrhenius Equation
- R: gas constant value is 8.3144598(48) J mol−1 K−1 - If the temperature was to increase to infinity, then the exponent would have a magnitude less than 1. - However; note the presence of a negative sign. As the magnitude of the exponent gets smaller, meaning more towards zero, rate constant actually increases.
Zero-Order Reaction
- Rate of formation of product is independent of changes in concentrations of any of the reactants. - k has units of M/s - k = - slope - Temperature and the addition of a catalyst are the only factors that can change the rate of a zero- order reaction. - addition of catalyst = lowers the activation energy = inc. k value
Atomic Radius
- Refers to the size of a neutral element. - Zeff increases left to right across a period, as a result atomic radius decreases from left to right across a period. - Increases down a group.
Gay-Lussac's Law
- Relates pressure to temperature - similar to charle's law : V/ T
Ion Product (IP)
- Same equation as the solubility product constant. - Unsaturated: IP < Ksp - SuperSaturated IP > Ksp - Saturated at equilibrium: IP = Ksp
Ionic Radii
- Size of a charged species - The largest nonmetal ionic radii and the smallest metallic ionic radii exist at the metalloid boundary.
Way in which solubility of a compound can increase
- Solid phase = increase the temperature - Gas phase = decrease temperature or inc. pressure
Electrolyte
- Solutes that enable solutions to carry currents - Ionic compounds such as NaCl, and KI. - Highly polar covalent bonds - Dissociate into ions when dissolved
Complete Ionic Equation
- Spectator ions = Nitrate = simply remain in the solution unchanged - Compounds such as polyatomic anions that retain their charge before and after reactions; these are usually spectator ions.
Galvanic (Voltaic) cells
- Spontaneous; release energy to the environment - Free energy change is negative, so Electromotive Force (emf or Ecell) must be positive - Commonly used as batteries. - Movement of electrons results in a conversion of electrical potential energy into kinetic energy.
Ground State of an atom
- State of lowest energy (n=1), in which electrons are in the lowest possible orbitals. - Bohr's Nobel prize winning model
Heisenberg Uncertainty Principle
- States that is it is impossible to know both an electron's position and its momentum exactly at the same time.
Hund's Rule
- States that subshells with multiple orbitals (p, d, f) fill electrons so that every orbital in a subshell gets one electron before any of them gets a second one.
Critical Period
- Temperature and Pressure where liquid and gas are indistinguishable and heat of vaporization is zero
Boyle's Law
- Temperature and the number of moles are held constant. - Inverse relationship between pressure and volume. - As pressure increases, volume decreases
Ionization Energy
- The amount of energy necessary to remove an electron from the valence shell of a gaseous species. - It is lowest when removal of the electron results in a complete shell or subshell; highest when the removal of the electron causes disrupts a complete shell. - Increases from left to right a cross a period. - 1st ionization energy < 2nd < 3rd - Highest ionization energy = Most exothermic - Ionization constant for weak acids is less than 1 (ex; 1.8*10^-5; only a very small amount dissociates in water)
Dynamic Equilibrium and reversibility
- The rate of the forward reaction equals the rate of the reverse reaction, entropy is at a maximum. - Links to the concept of thermodynamics and kinetics.
Collision Theory of Chemical Kinetics
- The rate of the reaction is proportional to the number of collisions per second between the reacting molecules. - Not all collisions result in a Chemical reaction - Effective collision = leads to product - Greater the concentration of the reactants, greater the number of effective collision - Z : total number of collisions; F: fraction of collisions that are effective
Medium
- The rate of the reaction may also be affected by the medium in which it takes place. - Generally, Polar solvents are preferred because their molecular dipole tends to polarize the bonds of the reactants, thereby lengthening and weakening them, permitting the reaction to occur faster.
Rate Determining Step
- The rate of the whole reaction is only as fast as the rate determining step. - Slowest step in any proposed mechanism - AB is the intermediate
Gibbs Free Energy
- Thermodynamic Potential - Spontaneous: Negative; Exergonic; ex) utilization of ATP; Enthalpy must be negative and entropy must be positive - Non-spontaneous: Positive; Endergonic - Free energy of the product can be raised or lower but not the activation energy value. - Delta G is temperature dependent when Delta H and Delta S have the same sign. - Negative Delta H and Positive Delta S = always spontaneous.
Coordinated covalent bond
- This represents the donation of a shared pair of electrons from a lewis base (H2O) to a lewis Acid (H+, electron Acceptor)
Carbonate
- Trigonal Planar: no lone pair - Double bond with one of the oxygens
Atomic Emission Spectrum
- When electrons return from the excited state to the ground state, they emit an amount of energy that is exactly equal to the energy difference between the two levels.
Atmospheric Pressure
- When the external air exerts a higher force than the mercury, the column rises
Daniell Cell / Galvanic cell
- Zinc is the anode and copper is the cathode; each electrode is bathed in an electrolyte solution containing its cation and sulfate. - Salt bridge allows the exchange of cations and anions. KCL or NH4NO3. - Electrons flow from A to C ( anode to cathode)
Oxidizing agent
- causes another atom in a redox reaction to undergo oxidation and itself reduced. - Oxygen and Halogens - Table 11.1 gen chem
Reducing Agent
- causes another atom in a redox reaction to undergo reduction and itself oxidized. - Metal ions and hydrides (H-) - Table 11.1 gen chem
Voltmeter
- emf of the cell can be measured - Potentiometer is a kind of voltmeter that draws no current and gives a more accurate reading of the difference
Boiling Point Elevation
- i (van't Hoff Factor) number of particles in which a compound dissociates in solution - Kb proportionality constant for a compound - m : molality = moles/ kg
Osmotic Pressure
- i (van't Hoff Factor) number of particles in which a compound dissociates in solution - M: Molarity - R: Ideal Gas Law .0821 L* atm/ mol * K -
Oxidation
- loss of electrons - e+ is on the product side
Angular Momentum of an electron orbiting
- n is the principal quantum number - h is planck's constant = 6.626*10^-34 J*s - Part of Bohr Model - L = n-1
Ka
- ratio of products to reactants - Greater than 10^-7, solution contains more H+ which makes it acidic.
Acid Dissociation Constant
- smaller Ka = weaker the acid - less it will dissociate - Ka < 1 = weak acid
Base Dissociation Constant
- smaller Kb = weaker base; Kb <1 - less it will dissociate - Nonionic weak bases are exclusively amines -
Isoelectric focusing
- technique used to separate amino acids or polypeptides based on their isoelectric point (pI). - Positively charged AA ( protonated at the solution's pH) will migrate to the cathode - Negatively charged AA ( deprotonated) will migrate towards the anode.
Standard Temperature and Pressure (STP)
- used for ideal gas calculations - 273 K or 0 C - a mole of ideal gas = 22.4 L
Ways to produce Hydrogen
-Reforming fossil fuels -Electrolysis of water ------Use electricity to split water into O2 and H2 -High Temperature Electrolysis -Biological processes
Born-Haber Cycle Steps (NaCl)
-Sublimation ΔHs (Solid to gas) Na(s)---Na(g) - Dissociation ΔHd (Molecule to Atom) 1/2 Cl2------- Cl(g) - Ionization (I) (Loss of Electron) Na(g)----Na+(g) + e- -Electron Affinity (E) (Addition of electron) Cl(g)-----Cl-(g) -Crystal Formation (U) (Lattice Energy)Na+ +Cl- ------ NaCl
If the complex is an anion (⁻), then the metal ends with the suffix __________
-ate
The names of anionic ligands always end in
-o
Born-Haber Lattice Energy Equation (NaCl)
-ΔHf = ΔHs + I + 1/2ΔHd+E-U ΔHs = Heat of sublimation of the sodium atom ΔHd = Heat of dissociation of the molecular chlorine. I = Ionization energy of the sodium E = Electron affinity of the chlorine (g) atoms. U = Lattice energy of sodium chloride
What is a unit cell? Relates to lattice? Seven basic unit cellls
...
Draw the orbital splitting diagram for [Cu(py)4]+ how many unpaired electrons are there?
0 unpaired all filled with pairs of electrons
What is the magnetic moment for [Ni(CN)4]2-?
0 μB
When ψ = 0 what is the probability?
0, this is called a node
A lattice point in the body of, that is fully inside, a cell belongs entirely to that cell and counts as ____
1
Gas Pressure units
1 atm = 760 mmHg = 760 torr = 101.325 kPa
simple cubic structure
1 atom/ unit cell
Solving for unit Cell
1) MW/Avagodos #= Average Mass 2) Density/Average Mass 3) Convert length to cm3= Volume of Unit cell 4) 1cm3/V of unit cell 5) 2 answer/4 answer= Atoms in unit cell
Name 4 Schottky defects?
1. A vacant atom site in a metal alttice 2. A vacant cation and anion site in an MX lattice 3. Two vacant cations and a vacant anion site in an M2X lattice 4. A vacant cation and two vacant anion sites in an MX2 lattice.
What is the effect of charge on the complex
1. Greater electrostatic attraction 2. M-L bond length reduces 3. Ligand orbital overlap increases which destabalises the d orbitals to a greater extent 4. Higher charge means a greater value for lambda
Improper axis (Sn)
1. Rotation by (360/n)° 2. Reflection in plane perpendicular to rotation axis
Name 3 uses of D2O.
1. Solvent in1H NMR 2. Moderator in nuclear reactors 3.Absorbtion of neutrons
What are the four types of sites in a lattice?
1. Unique central position 2. Face site (the ion shared between two unit cells) 3. Edge sites (the ion shared between four unit cells) 4. Corner (the ion shared between eight unit cells)
why is it that the larger the second and third row TM's the more likely they are to be inert?
1. there is less steric hinderance and therefore less tendancy for a given ligand to be forces from the coordination sphere 2.2nd and 3rd row metals are often more highly charged leading to stronger M-L bonds meaning they are less likely to undergo removal or substitution 3. from a covalent perspective, the larger metals use 4d and 5d orbitals which extend further out towards the ligand resulting in a higher degree of overlapping therefore increasing bond strength
Electron carries a charge
1.6 * 10^-19 coulombs (C) per electron
seven crystal systems
1.cubic 2.hexagonal 3.trigonal(rhombohedral) 4.tetragonal 5.orthorhombic 6.monoclinic 7.triclinic
A lattice point on the face is shared by two cells and contributes ________ to the cell
1/2
A lattice point on the edge is shared by four cells and contributes______
1/4
A lattice point at a corner is shared by eight cells and contributes_______
1/8
What is the velocity of light?
2.998 x 10^8 ms-1
body-centered cubic
2atom/unit cell
Maximum number of electrons within a shell
2n^2
BBR3464 is trinuclear , indicating that it consists of
3 Pt(II) atoms
{skip} How many different stereoisomers are there for M(AA)2de?
3 isomers: λ, Δ, and trans all the Δ can be arranged to same appearance..are same as other Δ's true for λ too
Lattice Structure
3d arrangements vary depending upon the sizes and charges of the ions
projection diagram
3d to 2D
Hexagonal Close-packed
3rd layer over 1st layer atom, 6 adjacent atoms in same layer ABABAB Pattern
Calculate the effective nuclear charge for irons 3s and 3s electrons
3s: 14.75 4s: 3.75
The visible spectrum lies between
400-700
fyi with metal ligand (acid base) interaction. identify lumo and homo. {hard} explain concept behind sigma donor and pi acceptor interactions in Oh complex!...and how does this affect Δo??
4s+4p on metal are actually the lumo, bc higher energy than 3d σ donors (Ag, Eg, T1u) on ligand are the homo, bc they donating e's ...if really want to bake ur noodle, know that ligand also has lumo that high enough energy to accept e's from d orbital of metal..and actually has symmetry like T2g...kind of like double acid base thing results in greater split (Δo larger) this extra interaction explains stability of carbon monoxide bond to Hb
For transition metals we can have up to __________ unpaired electrons
5
How many isomers are for octahedral structure M(AA)(BB)de? ~AA & BB are bidentate ligands, d & e are monodentate ~draw so AA is are in back
6 total ~For 2 Δ isomers on lower left, redraw to look like propeller by viewing from 10°clock ~For 2 λ isomers on lower right, redraw to look like propeller by viewing from 2°clock
How many stereoisomers are there for octahedral compound Ma2b2c2 (pic on answer) where a,b,c are monodentate ligands?
6 total (4 diastereomers, 2 enantiomers) 1. a-a, b-b, c-c 2. a-b, b-c, c-a <-2 stereoisomers (pair of enantiomers)...see pic 3. a-a, b-c, c-b 4. b-b, a-c, c-a 5. c-c, a-b, b-a
First step to creating MO diagram is to make reducible representation. What is reducible representation (Γ GO) for ligands of octahedral complex? What symmetry of the 6 ligands? (use characters from top row of Oh character table...E, 8C3, etc)
6C2 axis goes in btw the ligands..so no ligands on this axis = 0 this is essentially the representation for the σ donors Ag (1L) + Eg (2L's) + T1u (3L's)
Octet
8 electrons in outer shell are usually stable and unreactive
Jahn-Teller effect least likely to be relevant when this # e's in d orbitals? (a) 7 (b) 8 (c) 9
8...even number e's...even distribution, so no distortion.
How is cubic close-packing (ccp) arranged?
ABCABC...
Standard Free Energy Change
= -RTLnKeq - nFEcell = RT ln Keq - If E is positive then Keq is positive. this means that Keq is greater than 1 and that the equilibrium lies to the right ( products are favored)
Ionic Bond
A chemical bond resulting from the attraction between oppositely charged ions.
Ionic Compound
A compound composed of positive and negative ions that are combined so that the numbers of positive and negative charges are equal.
What is a superoxide?
A compound that contains the superoxide anion with the chemical formula O2-
Cubic Closed-packed
A crystal structure compose of the close-packed atoms with the stacking ABCABCABCA...
Bohr model of the atom
A dense positively charged nucleus is surrounded by electrons revolving around the nucleus in orbits with distinct energy levels.
What property classifies a particular ligand as ambidentate?
A ligand with two potential donor atoms, both cannot bind simultaneously. Become linkage isomers
A set of hybrid orbitals provides...?
A set of hybrid orbitals provides a bonding picture for a molecule in terms of localized sigma-bonds
Amorphous Solid
A solid made up of particles that are not arranged in a regular pattern
Crystalline
A solid that is made up of crystals in which particles are arranged in a regular, repeating pattern
Hexagonally close-packed (Hcp)
ABA First and 3rd layers are directly above each other
How is hexagonal close-packing (hcp) arranged?
ABABAB...
Cubic close-center(ccp) or Face-centered cubic(fcc)
ABC 3rd layer is not directly above A or B
Peptide Bond
Acidic carboxyl group reacts with a basic amino group
Classification of Inorganic Drugs
Active Complexes Active Elements Active Ligands
What group is number 1 in the periodic table?
Alkali metals
What group is number 2?
Alkaline earth metals
Electrons in diamagnetic molecules are?
All Paired
Why is geometric isomerism impossible for tetrahedral complexes?
All corners of the tetrahedron are adjacent to one another
What is a diamagnetic?
All electrons are spin-paired. (Only low spin d⁶ and d¹⁰ octahedral complexes)
If there is more than one ligand type present, how are they ordered?
Alphabetically, ignoring the prefixes such as di and tri
Standard Gibbs free energy from reaction quotient
Also = RT Ln Q/ Keq
Why are chelate rings more stable in metal ion complexes?
Because both of the coordinate bonds are with the same metal so both need to be broken at the same time for the ligand to leave the complex this is why bidentate ligands are more stable than monodentate
Oxidation/Reduction Reactions
Also called Redox reactions Oxidation: loss of e-; an oxidation number refers to # of e- given up; a positive oxidation number = the number of e- given up, eg- iron=Fe2+ or Fe3+ Reduction: gain of electrons, a reduction number indicates number of electrons gained. Elements can exist in several different oxidative states: -ous such as ferrous Fe2+ is a lower oxidative state than ferric compound Fe3+ (but this is old terminology). Now- Fe3+=iron III cation, or Fe2+=iron II cation. Often happens in liver via drug metabolism
Inorganic Antacids
Aluminum Hydroxide Calcium Carbonate Magnesium Hydroxide Sodium Bicarbonate Calcium Citrate Calcium Tartrate
What is the driving force for the formation of square planar geometry?
An increase in dz stabilization energy
Polyatomic Ions
An ion, charged particle, that contains 2 or more atoms linked by covalent bonds. Remove a hydrogen ion from H2O and leave behind the electron pair of O-H. The single hydrogen becomes positive, hydroxide has one extra electron now giving it a negative charge, OH-. Remove a hydrogen from carbonic acid- H2CO3 Bicarbonate ion: HCO3- and remove another hydrogen and get CO3-
Dalton
Atomic mass unit (amu); Also called a Dalton; Is a unit of mass; Approximately equal to mass of a proton or neutron (1amu); an e- is so much lighter than either a proton or neutron that its mass is generally ignored
Various Isotopes of Hydrogen
Atoms of the same element have the same atomic number (Z= 1), but may have varying mass numbers (A= 1, 2, 3,)
Octet Rule
Atoms undergo reactions in order to attain a noble gas electronic configuration with 8 outer shell electrons. Atoms seek to attain a stable configuration with filled s and p subshells eg Na has 1 e- in outer shell and Cl has 7 electrons in outer shell so Na will give up/lose its 1e- and Cl- will gain that electron. Na will acquire a + charge and has one e- less than it has protons; Cl- will gain a negative charge with 1 more e- than it does protons
Why are tetrahedral complexes always high spin?
Because delta t is never large enough to offset the pairing energy P
Why is a 2d orbital not possible?
Because n = 2 l can only equal 1 and 0. when l =0 there is an s orbital and when l =1 there is a p orbital.
Why are tetrahedral low spin states rare for 1st row transition metals?
Because ∆t is usually less than the electron pairing energy
How could you convert transmittance into absorbance
Beer lambert law
bidentate? example?
Bidentate = when 2 binding sites on ligand interact with metal atom e.g. Enthlenediamine (en) :NH2-CH2-CH2-H2N: ...the 2 nitrogen atoms (donate lone pairs) can coordinate w/metal atom
How do you calculate bond order?
Bond Order = (Number of electrons in bonding MOs - Number of electrons in antibonding MOs)/2
Covalent Crystals (define and example)
Brittle, poor conductor (except diamond), high melting point. Example: Diamond C, SiO2 (Quartz)
We established that reduction of Ru+3 more likely to happen with CN- as ligand (than with h2o). What effect is CN- having? (stabilizing Ru+2 or Ru+3?) Is this consistent with what we know about cyanide as good π acceptor?
CN- makes reduction of Ru+3 more likely...bc E° = +0.85 is ↑...so CN- is kinda favoring the product Ru+2 this is consistent with what we know about cyanide as good π acceptor...wants to hook up with more e- rich product (Ru+2)
carbon monoxide binds better to Fe+2 or Fe+3? why?
CO binds better to Fe+2 Fe+2 has more electrons, so easier give electrons to empty π orbitals on carbon monoxide
What ligands appear highest (strong field) in spectrochemical series and tend to interact strongly with orbitals of transition metals to cause large splitting of d orbital energies (favor low spin complexes)?
CO, CN- > phen > NO2- > ethylenediamine
Flourite Structure
CaF2, UO2, LaH2 AB2 FACE-Centered Cube F- occupies all Tetrahedral Holes** Coordination # (8,4) CCP
Pervskite Structure
CaTiO3, SrTiO3, PbZrO3 ABC3 (A) Cations are surrounded by 12(C) anions (B) Cations are surrounded by 6(C) anions (B) Cations occupy all Octohedral Holes
HCl reacts with CO_3^2- to form:
Carbon dioxide gas
Reducing Agents
Causes another atom in a redox reaction to undergo Reduction and itself is oxidized.
Oxidizing Agents
Causes another atom in a redox reaction to undergo oxidation and itself is reduced.
Ions
Charged particle bc it contains unequal numbers of protons and electrons. Cations: a charged atom, an ion, that has a positive charge; groups 1&2 metals on far left, Na+ and Ca++ Anions: ion that has - charge, groups 6&7 nonmetals on far right, Cl-
Chemical Compound
Chemical substance formed by joining together atoms of 2 different elements. 2 hydrogen atoms bond with 1 oxygen atom to make H2O.
If a molecule has a point of Inversion then it CANT be _____
Chiral
HCl
Cinfv
SO
Cinfv
What is geometric isomerism?
Cis (same) and Trans (different) isomerism AND: Mer (same plane 90-90-180) and Fac (different plane 90-90-90) isomerism
What type of isomers can square planar geometry posses?
Cis- and trans-isomers (geometrical isomers)
What type of isomers can tetrahedral geometry posses?
Cis- and trans-isomers (geometrical isomers) and R- and S-isomers (optical isomers)
What type of isomers can octahedral geometry posses?
Cis-, trans-, fac- and mer-isomers (geometrical isomers) and R- and S-isomers (optical isomers)
what is cisplatins mode of action?
Cisplatin is thought to bind to DNA at guanine N(7), complexation with Pt causes the helix to bend and partially unwind as a result causing it to not be replicated, this bending also causes it to be recognised by HMG (high mobility group) proteins that bind to the bent DNA and facilitate cell death
Consider "chelation effect" on Gibbs free energy (ΔG = ΔH - TΔS) in reaction... Co(NH3)6 + 3en <--> Co(en)3 + 6NH3 What happens to ΔH? ΔS?
Co(NH3)6 and Co(en)3 both consist of 6 nitrogens binding to cobalt...similar acid-base interaction...so enthalpy isn;t changing much. However, have more molecules on right. Entropy is increasing ("more disorder") = ΔS positive! Therefore, think of chelation as entropically driven process! Displacing monodentate ligands, creating more molecules!
what is the formula for pentaamminecarbonatocobalt(III) chloride
CoCO3(NH3)5]Cl
What is homonuclear?
Covalent bonds formed between two atoms of the element (diatom) or molecules that contain one type of element or elements with similar energies.
Difference between amorphous solid and crystalline solid
Crystalline solids have a specific arrangement while amorphous solids have no arrangement
SOCl2
Cs
H2C--CH2
D2H
Allene
D2d
Ethylene
D2h
(CO3)2-
D3h
BF3
D3h
Eclipsed ethane (C2H6)
D3h
PCl5
D3h
What is the point group of PCl5?
D3h
(AuBr4)-
D4h
XeF4
D4h
what ligand related to EDTA is used to treat plutonium poisoning
DTPA, an octodentate ligand
Solid
Definite shape and volume
Particles of Atoms
Dense, positively charged mass at the center of an atom where P and N are located. Shell Energy Levels Orbitals
Lattice Energy
Depends on size and charge of ions. Example: Na+ Cl- vs. Na+ Br- (Smaller ion, higher lattice energy) Cl has a larger radius. Example: MgO+2 O-2 vs. Sc+2 N-3 (higher charge = higher lattice) N-3 is more electrostatic.
Dien
Diethylenetriamine NH2CH2NHCH2NH2
provide an example of a chelating agent used to treat humans that have been exposed to polonium-210
Dimercaprol or alternatively HoEtTTC, a derivative of DDTC
CO2
Dinfh
N2
Dinfh
Valence Band Theory faults
Does not explain why complexs are colored when transition metals have intense color
What is the point group of CO2?
D∞h
How do you calculate the energy of a photon?
E = hv E in J h in J s v in Hz (s-1)
how many binding sites does edta have (ethylenediaminetetraacetate) ? ?_dentate?
EDTA is a hexadentate ligand with 6 lone pairs of electrons - all of which can form co-ordinate bonds with the same metal ion. ...but only 1 oxygen in each acetate binds bc of geometric constraints
What elements can have more than 8 electrons in their outer shell
Elements in the second row and subsequent rows can expand their octet
What are the two types of stereoisomerism that metal complexes can have?
Geometric Isomerism and Optical Isomerism
According to ligand field theory, when d orbitals of metal ions are placed in octahedral complex of ligand electron pairs, any electrons in these orbitals are repelled by field. What does this mean for symmetry of d orbitals? What symmetry (Ag, Eg, Tg) do dx2-y2 and dz2 orbitals have? What symmetry do dxy, dzy, dxy orbitals have? What causes energy difference (Δo)?
Eg symmetry - for dx2-y2, dz2 orbitals of metal atom..which are directed at surrounding ligands and raised in energy ...E symmetry is always doubly degenerate T2g symmetry - for dxy, dxz, and dyz directed btw ligands are unaffected by "field" ...remember distinction btw 3 axes is arbitrary so makes sense that would be T symmetry as this symm is always triply degenerate The result energy different is Δo. Um octahedral electrostatic field of ligands raises their energy...see next card for details.
Ions in solutions- Equivalency
Electrolytes: substance that conducts electricity when dissolved in H2O. Ion concentrations are measured as equivalents: Na has a charge of +1 and molec weight of 23g therefore monovalent Na+ of 23g (1mol) is 1eq; Ca2+ is bilvalent and weight 40g therefore one equivalent of Ca++ is 20g or 0.5mol. Equivalents of an ion in solution is the # of moles * charge (valence) mEq of an ion is 1/1000 of an equivalent therefore 1mEq is 0.001 Eq and 1Eq=1000mEq.
Cloud surrounding nucleus
Electron cloud e- (negative charge, 1-) number of electrons = number of protons
What is the Aufbau principle?
Electrons orbiting one or more atoms fill the lowest available energy levels before filling higher levels. In this way, the electrons of an atom, molecule, or ion conform to the most stable electron configuration possible.
What are bonding molecular orbitals?
Electrons that spend most of their time between the nuclei of two atoms stabilize the molecule.
What are antibonding molecular orbitals?
Electrons that spend most of their time outside the nuclei of two atoms decrease the stability of the molecule.
What is MO theory?
Energy diagrams corresponding to the bonding and antibonding electrons in a molecule. Electrons will fill according to the energy levels of the orbitals, with the lowest energy orbitals first. Can illustrate the type of bonding between elements by comparing electron contributions, ie. covalent, polar, ionic bonds.
For low spin configuration to occur
Energy difference my be greater than pairing energy
Lattice
Energy released when one mole of an ionic crystalline compound is formed from gaseous ions
en
Ethylenediamine NH2CH2CH2NH2
When do extrinsic defects occur?
Extrinsic defects result from the addition of dopants.
Force of Attraction equation
F = q1q2/r2
Wavefunction can only be positive, true or false?
False, it can be positive or negative ψ2 (probability) however can only be positive
T or F: d-electrons closer to the ligands will have lower energy than those further away which results in the d-orbitals splitting in energy
False: d-electrons closer (e.g. pz2, px2-y2) to the ligands will have a HIGHER energy than those further away which results in the d-orbitals splitting in energy
Periodic Table main group
Far Right- larger groups: Nonmetals- nonconductors of heat and electricity, tend to form anions if they ionize. Left Side- Metals: good conductors of heat and electricity; tend to react chemically to form cations by giving away e-
Iron [26] can be Fe+2 or Fe+3. What is electron configuration? When transition metals like iron ionize what orbital do they lose their e's from first?
Fe: 1s2 2s2 2p6 3p6 4s2 3d6 ...when ionize, lose from s (4s?) orbital first! Fe+2: 1s2 2s2 2p6 3p6 _ 3d6 ...so equivalent to [Ar] + 3d6 Fe+3: 1s2 2s2 2p6 3p6 _ 3d5
Ferrocene has two η_? cyclopentadienyl ligands
Ferrocene has two η5 cyclopentadienyl ligands
What is the covalent radius?
For an atom X, the value of the single bond __________ radius is half of the internuclear separation in a homonuclear X-X single bond.
Tetrahedral Coordination Complex is always ___________________
HIGH SPIN
What group is number 17?
Halogens
Octahedral d⁰ to d³ have __________ spin only and the diagrams look like
High
Octahedral d⁸ to d¹⁰ have __________ spin only and the diagrams look like
High
Weak Field Ligand=
High Spin
Lattice Formation
Highly organized state in which solid molecules align themselves.
Question: How do you redraw structure (flip flashcard) to make it resemble the propeller model? Is it λ or Δ?
How do you redraw structure to make it resemble the propeller model? Is it λ or Δ?
Valence Bond Theory
Hybridization of d orbital of the central ion creates vacancies able to accommodate one or more pairs of unshared electrons on the ligands.
What is Schödinger's equation?
Hψ = Eψ
What is the effect of the metals electronic structure on coordination number?
If the oxidation number is high, the metal has fewer d electrons and can therefore accept more electrons from ligands. These metals tend to have higher coordination numbers, while metals with lots of d electrons, such as those on the right side of the periodic table, tend to have fewer coordination numbers.
What is orbital degeneracy and what is the theorem called?
If there is choice as to where an electron can go then the orbital is said to be degenerate This is from the Jahn-Teller Theorem
What is Jahn-Teller Distortion?
If there is orbital degeneracy then the geometry of the complex will distort to remove the degeneracy and achieve a lower energy
As a ligand approaches the metal ion, the electrons from the ligand will be closer to some of the d-orbitals and farther away from others causing a loss of degeneracy. The electrons in the d-orbitals and those in the ligand repel each other due to repulsion between like charges. Thus the d-electrons closer to the ligands will have a higher energy than those further away which results in the d-orbitals splitting in energy.
In octahedral symmetry the d-orbitals split into two sets with an energy difference, Δoct (the crystal-field splitting parameter) where the dxy, dxz and dyz orbitals will be lower in energy than the dz2 and dx2-y2, which will have higher energy, bc the former group is farther from the ligands than the latter and therefore experience less repulsion. The three lower-energy orbitals are collectively referred to as t2g, and the two higher-energy orbitals as eg.
TQ. With d8 (8 electrons in d orbitals) metals in square planar complexes, what arrangement are metal d orbitals in? Which will be highest in energy? (pi bonding included) dz2 - a1g dx2-y2 - b1g dxy - b2g dxz, dyz - eg
In sq. planar ligand environment, 4 of 5 d orbitals end up lower energy and 1 (dx2-y2 or '2'b1g) is higher in energy ...the 4 lower are favored by d8 e- config (late transition metals, less sterics to favor Td) e.g. Pt+2, Pd2+, Rh+, etc ...whatever...i guess too clunky to form Td geometry
When do intrinsic defects occur?
Intrinsic defects occur in lattices of pure compounds.
Inversion center (i)
Inversion of a point x,y,z to -x,-y,-z
Predict and explain the periodic trends for ions and ionic compounds
Ionic Radius: Down and left increases. Melting point: Smaller radius= Higher Melting Point Lattice Energy: Larger radius= Lower Lattice
Electrostatic Attraction
Ionic bonding
Identify different types of solids and explain their forces
Ionic- Electrostatic attraction between cation and anion; Ionic bonds cations lose electrons and anions gain electrons Covalent- Ex. Diamond; Covalent Bonds sharing electron pairs Molecular- Same element, Conduct electricity; Van Der Waals forces Metallic- Metal properties; Metallic Bonding: attractive forces between delocalized electrons
if a molecular has a center of Inversion, none of its modes can be both ______ &_________
Ir & Raman active
What principle states that cannot have unequal occupation of orbitals with identical energies (e.g. if occupy 1 of 2 eg* degenerate orbitals) ? What happens as result?
Jahn-Teller effect- to avoid unequal occupation, molecule distorts so these orbitals are no longer degenerate
Antiflourite Structure
K2O, K2S, Li2O A2B FACE-Centered Cube CN (4,8)
Shape of an AB2L3 compound?
Linear
What shape are molecules with an sp hybridised central atom?
Linear
Draw 2-coordinate, what name do the structures have?
Linear Bent
Name the four types of constitutional isomerism?
Linkage, Coordination, Ionization, Solvate
Covalent Bonding of unlike atoms
Lipids Methane CH4 Good electrical insulators most not water soluble Lewis structure and line-bond structure- dots and lines used to represent outer shell electrons
Exchanging to unique ligands on octahedral complex doesn't necessarily make new isomer. Notice what happens (flip card) if rotate on C2 axis bisecting d & e.
Looks similar but d & e on opposite sides now. Chelate rings exchange positions but indistinguishable.
Strong Field Ligand=
Low Spin High DELTA
Molecular Crystals (define and example)
Low melting point, poor conductors, soft. Examples: Ar, CH4, CO2
Dilution Equation
M is molarity & V is volume
Dalton's Atomic Theory
Matter consists of definite particles called atoms, are indestructible, are identical in mass if of a particular element, are different masses if of different elements, and joining together whole particles atoms will form different compounds.
Explain Ionic bond and how it is formed.
Metal and Nonmetal (Electrostatic attraction between cation and anion) Cation loses electrons and anion gains electrons
Why is metals used in Medicine
Metals lose electrons to form cations and therefore are electron deficient. Biological molecules such as enzymes, DNA and peptides are electron rich and hence complex with metals.
What do metals with low melting points not adopt and what groups have the lowest melting points?
Metals with low m.p. do not adopt close-packed structures. Groups with lowest m.p. are 1, 12, 13 (except Al), 14 and 15.
Electron Configuration according to atomic number
Mg12: 1s2, 2s2, 2p6, 3s2 Generally, the more electrons, the more orbitals, the more energy. eg: Hydrogen has low energy compared to that of Argon
Electrodeposition equation
Mnemonic: Calculating Moles of Metetal, It is Not Fun
Molecule<->Compound
Molecule-smallest quantity into which a substance can be divided without loss of that substance's characteristics. Compound-composed of 2 or more chemically united elements that form a substance differing in properties from those of the individual composition of elements.
Molarity
Moles of Solution/ Liters of Solution
High Spin=
More unpaired Electrons Small DELTA
What does close-packing of spheres results in?
Most efficient use of the space available.
Neutron
N- (No charge) Number of neutrons determines the isotope of the element (may or may not equal number of protons)
Give an example of an ambidentate ligand
NOO- because there is a lone pair on the N and O so either can be used to form the coordinate bond: this is selected using environmental factors
mEq and mosm
Na+ is one equivalent and univalent, and 1 mEq/L=1 mosm so 1mEq of Na(23g)=1mosm. Ca++ is bivalent so 1mEq/L will equal 0.5mosm so 2mEq/L=1mosm.
What happens when NaCl and CCl4 mixed separately with both i) Water ii) Hexane What happens when water and hexane are mixed together?
NaCl: i) dissolves ii) remains solid CCl4: i) will not mix ii) will mix because both have large dispersion forces Hexane and water: will not mix because hexane is nonpolar and water is polar
what is the formula for sodium amminetrichloroplatinate(II)
Na[PtCl3NH3]
What is the Pauli Exclusion Principle?
No two electrons in any system can have identical values for all quantum numbers : therefore there is a maximum of two electrons with opposite spins allowed
Electrons in paramagnetic molecules are?
Not all paired
Covalence
Number of bonds that an element forms. Hydrogen has a covalence of 1, Oxygen has covalence of 2, Nitrogen has covalence of 3. Outer shell electron + covalence = 8; the exception is Hydrogen
Draw the lewis structure for NO2-
O-N=O single bond O has 3LP and -1 charge double bond O has 2LP and no charge N has 1LP and no charge
high oxidation state metals are often found with
O/F ligands (hard acid to Hard base)
Draw 6-coordinate, what name does the structure have?
Octahedral
Shape of an AB6 compound?
Octahedral
What shape are molecules with an sp3d2 hybridised central atom?
Octahedral
What properties are shared for the first row of transition metals (d⁴ to d⁷ configurations)?
Octahedral complexes are high spin in M(II) oxidation state for all ligands except for strong field ligands (CN and CO and maybe N)
SF6
Oh
According to Jahn-Teller effect, octahedral molecule distorts self (so no longer degenerate) to avoid making empty degenerate orbital "jealous". How does it distort self...for example if dz2 orbital occupied, but dx2-y2 is not? How are energy levels affected?
Oh molecule elongates along z axis, bc e- density approaching along z axis = ↑ repulsion = dz2 now ↓ energy ....at same time, dx2-y2 sucked in = dx2-y2 ↑ energy
What is an allotrope?
One of two or more existing forms of an element: Graphite and diamond are allotropes of carbon.
What is paramagnetic?
One or more unpaired electrons.
Sp3 hybridization?
One s and three p atomic orbitals mix to form a set of four hybrid orbitals with different directional properties (no p orbitals)
Sp2 hybridization?
One s and two p atomic orbitals mix to form a set of three hybrid orbitals with different directional properties (double bond).
Sp hybridization?
One s atomic orbital and one p atomic orbital mix to form a set of two hybrid orbitals with different directional properties (triple bond, two p orbitals).
Antiferromagnetic
Opposite EQUAL Spin Negative on Curie Weiss Plot
the only two atoms with electronegativities in the specified range for a hard base are
Oxygen and fluorine eg O2-, F-, OH2, CO3 2- and PO4 3-
Proton
P+ (+1 charge) Number of protons determines the chemical element Number of protons = number of electrons
Periodic Table of Elements Structure
Period: horizontal Row Group: vertical column Main group: far right and far left Transitional metal group: Metalloids (semi-metals)- in middle of table, eg- silicon Lanthanide and actinide series: fall outside in a subgroup- f shell
What is the Schottky defect?
Point defect in a crystal lattice and arises from vacant lattice sites. Stoichiometry and electrical neutrality of the compound are retained.
Chelate
Polydentates that form a ring including the metal ion
Valence Band Theory purpose
Predict coordination complex structure
What is the VSEPR model?
Predicts the orbital and molecular geometry of species. It is based on the assumption that electron pairs adopt arrangements that minimize repulsion.
When you have a heterodiatomic molecule with one atom much more electronegative than the other, how do you draw its molecular orbital diagram? What effect does this have on the strength of the bond?
Put the most electronegative atom much lower in energy than the other This doesn't mean the bond is weaker because there are usually ionic interactions when electronegativities are very different
Shape of an AB3L compound?
Pyramidal
Mole
Quantity of of a chemical compound whose weight in grams equals its molecular weight, eg H2O=18grams=1mole
Paramagnetic
RANDOM
Ionic Radius
Radius of cation or anion
Symmetry plane (σ)
Reflection in the plane
Define Ligand Field Theory (LFT)
Represents the bonding, electron configuration and characteristics of metal complexes
Review MO diagram notes or see BH3 example in week 14 notes
Review MO diagram notes or see BH3 example in week 14 notes
Proper axis (Cn)
Rotation by (360/n)°
Linkage Isomer
Same Ligand bonds through two different Atoms {Co(CN)6} Can connected to N {Co(CN)6} Can connect with C
Ferromagnetic
Same direction Positive on Curie Weiss Plot
Shape of an AB4L compound?
Seesaw/seahorse
Structure of atom
Smallest and simplest piece that an element can be broken into while still maintaining the chemical properties. An atom is classified according to number of protons and neutrons in nucleus.
Shape of an AB5L compound?
Square based pyramid
Complexes with platinum [Pt (II)] are always what geometry
Square planar
Shape of an AB4L2 compound?
Square planar
What is other 'systematic' way to determine if λ or Δ?
Start with both rings as coplanar. Position one of chelate rings in back (horizontal). Figure out how move (CW or CCW?) other ring from coplanar orientation to current position! ...notice in pic rotating CCW as on C4 axis = λ remember we are not trying to determine rotation to get to coplanar, but from coplanar to whatever it looks like now
Proton, Neutron, Electron
Subatomic particles; Elementary particles from which atoms are made
Reducing Agent
Substance that causes a reduction by giving electrons. A reducing agent becomes oxidized (more positive). Sodium is the reducing agent- gives up electron; Chlorine is the oxidizing agent- accepts electrons. Na+ is now the oxidized cation and Cl- is now the reduced anion.
Ch4
Td
SiCL4
Td
SiF4
Td
Shape of an AB4 compound?
Tetrahedral
What shape are molecules with an sp3 hybridised central atom?
Tetrahedral
Draw 4-coordinate, what name do the structures have?
Tetrahedral Square planar
Coordination compounds typically in what geometry? Trigonal? C2v?
Tetrahedral (Td) Octahedral (Oh) Square planar (D4h)
For the first row transition metals (d⁴ to d⁷)
Tetrahedral complexes are all high spin Square planar complexes are all low spin
Polytypes
The THIRD close-packed layer can be layered two different ways -Hexagonally close-packed (Hcp) - Cubic close-center(ccp) or Face-centered cubic(fcc)
What does it mean if the stabilisation energy is negative?
The complex is stable because it has more electrons in lower energy orbitals
What does a small delta o mean?
The complex will have high spin
What does a large delta o mean?
The complex will have low spin
What causes a complex to be square planar and not tetrahedral?
The delta o value/ ligand type Tetrahedral = small delta o (Cl- < H2O < NH3/en) Square planar = big delta o (CN- > bipy > en/NH3)
What is VB theory?
The formation of a molecule arising from the sharing of electrons which, when they interact, create a hybrid orbital.
What is solvate isomerism?
The interchange of a neutral solvent for a negative ion e.g. [Cr(OH2)6]Cl3 and [Cr(OH2)5Cl]Cl2.H2O and [Cr(OH2)4Cl2]Cl.2H2O
What does solubility depend on?
The intermolecular forces in the compounds, like dissolves like
What is Hund's Rule?
The most stable electronic state is the one with the most parallel spins
For a neutral or basic ligand, the ligand is given what name?
The name of the molecule, eg. trimethyl phosphine and pyridine. Exceptions are aqua H₂O, ammine NH₃ and carbonyl CO
What are valence electrons?
The outermost electrons in the highest energy level *Totally filled d orbitals are not included in the valence electrons*
Lattice Point
The positions occupied by atoms, molecules, or ions that define the geometry of a unit cell
What did Heisenberg come up with?
The principle of uncertainty. We can not determine the velocity and position of a particle at the same time. The probability (Ѱ²) can be calculated with the wavefunction (Ѱ).
Unit Cell
The smallest portion of a crystal lattice that shows the three-dimensional pattern of the entire lattice
What is a unit cell?
The smallest repeating unit in a solid state lattice.
Melting Point
The temperature at which a solid becomes a liquid
Why are compounds containing Sc3+, Ti4+ or Zn2+ colorless?
Their metal ions have either an empty or a filled d subshell
What are core electrons?
They occupy lower energy quantum levels than valence electrons.
Colligative Property
Those that depend on the amount of solute present, but not the actual identity of the solute particles. - Ex) vapor pressure depression, boiling point elevation, freezing point depression
Rutile Structure
TiO2, MnO2 AB2 Cations only fill half the Octohedral Holes CN (6,3) (HCP)
Unpaired Electrons act as __________________
Tiny magnets
Dalton's Law of partial Pressure
Total Pressure of a gaseous mixture is equal to the sum of the partial pressure of the individual components.
What are the number of nodes for a 3d orbital?
Total number of nodes = 2 Angular nodes = 2 Radial nodes = 3 -2 -1 = 0
Shape of an AB5 compound?
Trigonal Bipyramid
What shape are molecules with an sp3d hybridised central atom?
Trigonal bipyramid
Draw 5-coordinate, what name do the structure have?
Trigonal bipyramidal Square pyramidal Pentagonal planar
Shape of an AB3 compound?
Trigonal planar
What shape are molecules with an sp2 hybridised central atom?
Trigonal planar
Draw 3-coordinate, what name do the structures have?
Trigonal planar T-shaped Trigonal pyramidal
Shapes of an AB3L2 compound?
Trigonal planar or Pyramidal or T-shaped
Probability is always positive, true or false?
True
T or F: Because of inherent symmetry of tetrahedron, the only isomers possible for tetrahedral complexes are chiral.
True
T or F: If molecule has plane of symmetry, then not chiral.
True
T or F: ligand environment dictates chemical property of metal center
True..
T or F: Ligands play role of Lewis base.
True: have at least one unshared pair of e's
Face-Centered Cubic Cell
Two atoms, A cubic unit cell with one atom on each of the six faces and one atom at each of the eight corners, coordination number 12.
Isoelectronic
Two different elements that share the same electronic configuration (ex K+, Ar)
What is isoelectronic?
Two species are __________ if they possess the same total number of electrons.
Shape of an AB2L compound?
V-shaped
Shape of an AB2L2 compound?
V-shaped
Metallic Crystals (define and example)
Variable hardness and melting point, good conductors. Example: All metallic elements, Na, Mg, Fe
What does this symbol ψ denote and what can its values be?
Wavefunction It can have positive and negative values
Atomic Weight
Weighted average of the naturally occurring isotopes of an element.
{skip} Iron ion form complex ions. Which ion: +2 or +3? Which orbital accepting electrons?
When Fe --> Fe3+ ion it loses the 4s electrons and one of the 3d electrons to leave. Now, be careful! The single electrons in the 3d level are NOT involved in the bonding in any way. Instead, the ion uses 6 orbitals from the 4s, 4p and 4d levels to accept lone pairs from the water molecules.
Conjugate Acid
When a base gains a proton
What is coordination isomerism? Give an example
When an anion and cation complec "swap" ligands e.g. [Co(NH3)6][Cr(CN)6] and [Co(CN)6][Cr(NH3)6]
What is Hunds rule
When more than one orbital has the same energy, electrons occupy separate orbitals with parallel spin
Hydrate Isomerism
When one molecule is water and switches in and out of complex. [CrCl(H2O)5]Cl2*H20 [CrCl(H2O)4]Cl2*2H20 Move around H2O molecules
What is ionization isomerism?
When the anion and ligand swap places e.g. [Co(NH3)5(SO4)]Br and [CoBr(NH3)5]SO4
What is linkage isomerism?
When the ligand stays the same but the atom forming the coordinate bond is different With the ligand NOO- either N or O can form the bond
Coordination Isomerism
When there are different complex ions that can be formed using the same molecular formula. Ligand attaches to another molecule
Can total CFSE be determined from ∆₀ and P values
Yes
Atomic Symbol
Z= atomic number (# of protons); A= atomic mass or mass number (weight[#protons + neutrons]); C= charge (+/-); #= number of atoms in a formula
Wurtzile Structure
ZnS, ZnO, BeO AB Fill Half Tetrahedral Holes CN (4,4) (HCP)
What is the electron configuration of these complexes? [Mn(CO)4]3- [Cu(py)4]+ [Cr(bipy)2ClBr]+ [VO(acac)2]
[Mn(CO)4]3- = d8 [Cu(py)4]+ = d10 [Cr(bipy)2ClBr]+ =d3 [VO(acac)2] = d1
At high temps,_________ is common for metals that are close-packed at low temps on account of the increase amplitude of ___________.
a bcc structure atomic vibrations
Ligands are coordinated to a metal centre to form
a complex
Primitive Cubic Cell
a cubic unit cell in which the lattice points are at the corners only.
Body Centered Cubic Cell
a cubic unit cell in which the lattice points occur at the corners and at the center. 2
a macrocycle can be defines as
a cyclic molecule with three or more potential donor atoms that can coordinate to a metal center
Molecular Weight
adding atomic weights, or mass number, of all elements in a molecule.
Excipients
additives that help stabilize the drug dispersion as well as increase the lifetime
law of symmetry
all crystals of the same substance posses the same elements of symmetry
In the ground state
all electrons are in their lowest energy positions
Explain basis for this spectrochemical series: I- < Br- < Cl- < OH- < RCO2 (acetate) < F- < H2O What do these have in common? What are we ranking here?
all potential π donors those on left (lesser) are weaker field, higher spin, smaller Δ, and more π donating tendency ...so OH- is below H2O bc has greater π donating tendency
angles of uni cell
alpha between c and b beta between a and c gamma between a and b
(NH₄)₂[Co(H₂O)₆](SO₄)₂
ammonium hexaaquacobalt(II) sulfate
a dissociative mechanism corresponds to
an sn1 reaction, in which the slow rate determining step is first whereby a M-L bond breaks forming a 5 coordinate intermediate, a dissociative mechanism only depends on the concentration of the original complex therefore reflects first order kinetics
Why is EDTA delivered as a calcium disodium salt in chelation therapy
as a free acid or just as a disodium salt, it will deplete the bodies own Ca levels since EDTA complexes strongly with Ca2+
What kind of electron structure do distorted complexes have
asymmetrical electron structure
with square planar coord complex (d4h), the symmetry of the d orbitals is more diverse. dz2 - a1g dx2-y2 - b1g dxy - b2g dxz, dyz - eg which do u think willl form [σ] bonding orbitals with ligands?
b1g (dx2-y2)...ligands coming in on axes a1g (dz2)...all ligands have an 'a' orbital evidently
What is E equivalent to?
c1 rotation of 360 degrees
According to Jahn-Teller effect, which eg* orbital is moved higher if dz2 orbital occupied, but dx2-y2 is not?
bc e- density approaching along z axis = ↑ repulsion = DZ2 NOW ↓ ENERGY! degeneracy is broken by the stabilization (lowering in energy) of the d orbitals with a z component, while the orbitals w/o a z component are destabilized (higher in energy)
Why are d orbitals pertinent to coordination complex?
bc in coord complexes it is d orbitals that are usually incompletely filled...so this is where metal valence e's are and where lumo/homo interaction occurs.
why does a high charge often result in a small size
because the remaining electrons are contracted towards the nucleus by substantial positive charge
Do dxy, dyz and dxz orbitals lie __________ the axes
between
If have π accepting ligands, is t2g nonbonding or what?
bonding MO?
pyridine and other ligands containing heterocyclic nitrogen atoms are classified as
borderline bases
What is the relationship between wavelength and frequency?
c = λv c in ms-1 λ in m v in Hz (s-1)
The only space in naming the complex is designated to separating the
complex and counter ion
Lewis acid base rxns in which METAL cation combines with lewis base result in formation of complex ions. What is complex ion? Why do transition metals have tendency to form them? What is coordinate covalent bonds?
complex ion = ion containing a central metal cation bonded to ligands (one or more molecules or ions) complex ions are crucial to many chemical and bio processes transition metals have incompletely filled d subshells - enables them to act as Lewis acids (accept e's) to ions acting as e-donors ...metal-ligand bond = coordinate covalent bonds
What is a coordination compound?
complex ion and counter ion
the macrocyclic effect is a phonomenon where
complexes containing macrocyclic ligands show higher stability constants than analogous acyclic (open chain) complexes
fyi how do u make reducible representation for Pi bond of ligand?
consider axis perpendicular to bonding axis have to account for x and y axis E =12 8C3 = 0 etc
What is coordination number of square planar molecule? octahedral?
coordination # for sq planar molecule = 4 " for octahedral = 6
soft acids and bases mostly participate in --- interactions
covalent, because their electron clouds are polarisable, thus allow the sharing of electron density
Ligands are __________ bonded to the metal centre
covalently
What do these stand for: Ccp lattice Hcp lattice Bcc structure
cubic close packed hexagonal close packed body-centered cubic system
for the majority of systems, successive formation constants
decrease in value, this can be explained statistically speaking as for each successive replacement of a ligand there are fewer to replace, steric hindrance may also be a factor if the substituting ligands are bulkier than the ligand (eg h2o) that they are replacing
chelators are classified based on ?
depending on number of donor atoms (binding sites to metal center)
what is the name of [Pt(CO)2(P(CH3)3)2]
dicarbonylbis(trimethylphosphine)platinum(0)
A molecule cant have an _______________ perpendicular to any axis of roation
dipole moment
A molecule cant have an _______________ perpendicular to any mirror plane
dipole moment
The strength of the ionic bond in lattice or lattice is ______________ to the charges on the ions and ____________ on the distance between the centers of the ions in crystal lattice
directly proportional, inversely
octahedral substitution reactions often follow a ---- mechanism
dissociative
what are the three types of ligand substitution reactions
dissociative, associative and the interchange mechanism
an ionic solid with_________ have much larger lattice energies compare to solids with ____________.
divalent ions(+2) , monovalent ions(+1)
Lewis Structure
dots expressed on elements and compounds represent # of electrons in outer shell
According to Jahn-Teller effect, which is moved higher on MO diag if dx2-y2 orbital occupied, but dz2 is not? (concerned with eg* level, t2g less important)
dx2-y2 = ↓ energy dz2 = ↑ energy degeneracy is broken by the stabilization (↓ in energy) of the d orbitals w/o a z component, while the orbitals with a z component are destabilized (↑ in energy)
In a tetrahedral complex, ligands interact more with
dxy, dyz and dxz
In an octohedral complex, ligands interact more with what orbitals
dx²-y² and dz²
What orbital(s) are required for an octahedral geometry
dx²-y² and dz²
Review: What do dz2 and dx2-y2 orbitals look like?
dz2 is along z axis and has donut around it dx2-y2 has directly on x & y axes
Which d orbitals (dxy, dz2, etc) have greater energy lvl ↑ when interact with ligand?
dz2, dx2-y2 get bigger energy boost...interaction stronger bc evidently ligands come in along axis resulting in σ interaction remember these two orbitals have lobes along the axes ..others like dxy are wedged between etc
What are the symmetry labels in a tetrahedral complex?
e and t2 no centre of symmetry so no g labels
What are the symmetry labels in an octahedral complex?
eg and t2g
Ionic Bonding
electrical reaction between a cation and an anion. Ionic compound groups include cations in groups 1,2,3 and anions in groups 6,7. electron transfer leads to greater stability and ionic bonds occur when metals and nonmetals react. Ionic bonds have high melting points, often are water soluble and form crystals at room temperature.
energy levels
electrons are in constant motion but confined to specific regions within the atom according to the amount of energy. The more electrons generally means more energy. Orbitals
Avagadro's number
electrons per 1 mol of electrons
Isotopes
elements can have different mass numbers depending on how many neutrons they have; atomic number (proton #) stays the same but the neutron number may differ. Hydrogen has 3 isotopes- protium, deuterium, titrium; chlorine has 2 isotopes- 35Cl and 37Cl (Atomic Mass=35.453 bc more exist in 35Cl form).
tetragonal
essential symmetry: 1 four-fold rotation restrictions on unit cell: a=b, alpha =beta=gamma=90degrees
hexagonal
essential symmetry: 1 six-fold symmetry restrictions on unit cell: a=b, alpha=beta=90, gamma=120
trigonal
essential symmetry: 1 three-fold rotation restrictions on unit cell: a=b=c, alpha=beta=gamma=not 90 degrees
monoclinic
essential symmetry: 1 two-fold rotation and/or mirror plane restrictions on unit cell: alpha=beta=90 degrees
orthorhobic
essential symmetry: 3 two-fold rotations and/or mirror planes restrictions on unit cell: alpha=beta=gamma=90 degrees
cubic
essential symmetry: 4 three-fold rotation axis restrictions on unit cell: a=b=c, alpha=beta=gamma=90
triclinic
essential symmetry: none restrictions on unit cell: none
According to Jahn-Teller effect, octahedral molecule distorts self (so no longer degenerate) to avoid making empty degenerate orbital "jealous". How does it distort self...for example if dx2-y2 orbital occupied, but dz2 is not? How are energy levels affected?
evidently Oh molecule spreads out along dx2-y2 axes (where electron repulsion occurs) and compresses on z axis dx2-y2 = ↓ energy dz2 = ↑ energy
Color arises from a solution due to:
ex) The color arises because nickel (II) ion has partially filled d orbitals and the electrons in the lower d orbitals absorb visible light to move to the higher energy level
Besides cis and trans isomers, what other classes of isomers can be seen in octahedral isomers in regards to geometrical isomers
fac (facial) and mer (meridional)
if none of 3 [identical] ligands are trans to eachother on octahedral molecule, is it meridonal or facial config?
facial
4s electrons are lost ----
first
Henderson- Hasselbalch Equation
for POH, it would be log of conjugated Acid/ base
When a metal complex forms, the equilibrium constant for the reaction is called the
formation constant
Element
fundamental substance that cannot be broken down chemically into a simpler substance; arranged on periodic table according to atomic numbers
Why are Cl- ligands considered labile (liable to change; easily altered)?
halides (F-, Cl-, Br-, I-) as ligands! have occupied p orbitals = π donor π donors (smaller Δ...ligand field split) as result halide complexes tend to have high spin configurations
the chloro ligand is regarded as a
hard bas (but not as hard as the F or O donor ligands)
Why are heavy metals often toxic?
heavy metal ions are soft acids and therefore prefer to bind to soft bases such as amino acids
In the M(III) oxidation state, octohedral complexes are likely to have a __________ spin because
high M-L bond length is shortened by a high charge on the metal center resulting in greater spin. Exception of Co³⁺ which has an observable low spin state.
Do high or low spin electrons have a greater magnetic moment
high spin
what is lumo and homo of CN-? (just look at answer)
homo is σ orbital with concentration of electron density on carbon lumo orbitals are 2 empty π* orbitals that can be used for π bonding with metal
Overall as we go down in a group, ionic radius__________and lattice energy________.
increases , Decreases
explain concept behind sigma donor and pi donor interactions in Oh complex!...and how does this affect Δo??
if t2g of ligand already filled (e.g. with chloride or halide ligand), can actually act as pi donor to metal! this results in t2g* (antibonding) being big man on campus which is higher in energy, and consequently Δo much smaller ...narrow split bc t2g* is closer to eg* above it
when will an associative mechanism show a pseudo first order reaction
if the entering ligand is H2O
Where do ethylenediamine, NH3, and NCS- appear on spectrochemical series?
in middle...σ donors only H2O < NCS- < NH3 < ethylenediamine
Magnetism in solids originates __________
in the magnetic properties of an electron.
Magnetic moment __________ with the number of unpaired electrons
increases
As the charge on oppositely charged ions __________, the electrostatic force of attraction _________ between them which results in high lattice energy.
increases, increases
As the lattice energy____________, the strength and stability of the crystal lattice ___________.
increases, increases
complexes which undergo slow ligand exchange are said to be
inert complexes
soft bases are characterized by
intermediate to high electronegativity and large size, leading to polarizability
soft acids are characterized by
intermediate to high electronegativity, large size and low charge (+1/2)
Born-Mayer equation
is an equation that is used to calculate the lattice energy of a crystalline ionic compound.
Ligand
is an ion or molecule that can have an independent existence
tetrahedral hole
is formed by a planar triangle of touching spheres capped by a single sphere lying in the dip between them.
Kapustinskii's equation
is used to estimate lattice enthalpies of ionic compounds and to give a measure of the thermochemical radii of the constituent ions.
what is a serious side effect associated with cisplatin
kidney damage
inert and labile are ---- terms
kinetic
What is the equation for the number of angular nodes?
l
What is the angular momentum quantum number?
l, can have integer values equal to (n-1) including 0 It determines the size of the orbital
Label the orbitals according to their l value
l=0 s orbital; l=1 p orbital; l=2 d orbital; l=3 f orbital
kineticaly speaking, the first dipositive row of TM's form --- complexes
labile most second and thirds row TM'S are inert
complexes that undergo rapid ligand exchange are said to be
labile complexes
in regards to polarizability, soft acids and bases are
larger and more easily polarised
Draw the orbital diagram for a tetrahedral complex
lecture 8
Draw the orbital diagram for an octahedral complex
lecture 8
Draw the orbital splitting diagram for a square planar complex
lecture 9
For electrons to be paired, repulsion energy must be
less than difference in energy between orbitals (pairing energy)
what is the difference between lewis acids and bases
lewis acids accept electron pairs whilst lewis bases are electron donors
Octahedral hole
lies between two triangles of spheres on adjoining layers. N#of spheres= N# of Octahedral holes
Amount of splitting depends on the
ligand field strength (according to spectrochemical series)
What theory is more of a MO type approach to coordination chemistry ?
ligand field theory = MO type approach to coordination chemistry (ligands + d orbital of metal center) i guess less focus on repulsion btw charges and more on symmetry of interacting orbitals
monodentate
ligand with one point of attachment
coordination sphere ?
ligands (ions) surrounds metal center in the solution etc
Low oxidation state metals are often found with
ligands such as carbon bonded carbonyl ligands (a soft base)
Ambidentate
ligands with more than one different donor
Complexes with a coordination number of 2 are
linear (sp hybridised)
Hard acids are characterized by
low electronegativity, relatively small size and high charge (>2+, Mn2+ is an exception)
For the second and third row transition metals, d⁴ to d⁷ octohedral complexes have
low spin even for weak field ligands. Pairing energy is much smaller due to the larger size of the 4d and 5d orbitals ie. repulsion is less.
If have 3 or fewer e's in d orbitals than no need for high vs low spin designation bc t2g (_ _ _) is a triplet. Let's say have 4 e's in d orbitals. Which has more πc (columbic energy): high spin or low spin?
low spin has more πc, bc of pair remember when more e's added, need to either pair them (low spin) or add to higher energy level (high spin) like eg*
For the second and third row transition metals, d⁴ to d⁷ tetrahedral complexes are
low spin. Low repulsion due to the large size of 4d and 5d orbitals
What is advantage of low spin? High spin? When is one favored over the other?
low spin: no need to jump (Δo) to higher energy lvl (eg*) high spin: less πc, more πe so comes down to Δo vs πe
Disulphide (S-S) linkages formed between neighboring cysteine residues are important in
maintaining the tertiary structure of proteins and enzymes
a single crystal
means a perfect crystal
How do the quantum numbers depend on each other?
ml is dependant on l and l is dependant on n
What is the magnetic quantum number?
ml, its allowed values are -l to +l including 0 It determines orientation in space of the orbital
Law of Definite Composition
molecule of a substance is always made up of the same number of the same atoms in the same configuration, or more simply put, a compound is formed by a combination of elements in a defined proportion
ligand with only one binding site (or donor atom) are known as ? examples?
monodentate e.g. H2O or NH3 so these aren't chelators? no, they are not
What is the equation for the total number of nodes?
n - 1
What is the equation for the number of radial nodes?
n - l -1
What is the principle quantum number?
n, can have integer values but *not 0* It determines the size of the orbital
In the excited state
one or more electrons are excited to a higher energy orbital leaving valency in a lower energy orbital
Linkage isomers arise when
one or more of the ligands can coordinate to the metal center in more than one way (eg. ambidentate ligand NO₂⁻ nitro/ONO⁻ nitrito)
How many stereoisomers are there for octahedral compound Ma3b3 (pic on answer) where a,b are monodentate ligands? To figure out think of Oh molecule as 3 linear bonds / ligand combos (a trans a, b trans b, etc)
only 2 stereoisomers 1. a-a, b-b, a-b (pic) 2. a-b, a-b, a-b fyi: neither are chiral, bc both have plane of symmetry
Para-hydrogen (H2)
opposing nucleus spins Low temp
chelate ring?
p.328 when bi- or multidentate ligand binds to metal form closed "ring"...cyclic structure = chelate ring
Explain crystal field theory: (be vague...some controversy over definition)
p.369 electrostatic approach to coordination chemistry in which ligands are thought of as approaching negative charges e's come in and increase electron densitry = ↑ energy level
dx²-y² and dz² orbitals are __________ and on the cartesian coordinates
parrallel
The probability of finding a particle in any region of space is...?
proportional to the square of the wavefunction
what is the central metal in a heam unit, provide its oxidation state also
protoporphyrin IX being Fe(II) based
As a general rule, ligands with an O exert a __________ ligand field
weaker
Consider the following reduction potentials after swapping ligands: H2O vs. CN- . Which more likely to happen? Fe3+(aq) + e- ---> Fe2+ E° = +0.77 [Fe(CN)6]3- + e- ---> [Fe(CN)6]4- E°=+0.36
reduction potential greater in aqueous environment (E°=+0.77) = more likely to happen! CN- makes reduction of Fe+3 less likely...bc E° = +0.36 is lower
Consider the following reduction potentials after swapping ligands: H2O vs. CN- . Which more likely to happen? Ru3+(aq) + e− ⇌ Ru2+ E° = +0.25 [Ru(CN)6]3− +e− ⇌ Ru(s) + [Ru(CN)6]4− E°=+0.85
reduction potential greater w/cyanide as ligand (E° greater) = more likely to happen! CN- makes reduction of Ru+3 more likely...bc E° = +0.85 is ↑
in regards to polarizability, hard acids and bases are
relatively compact and non-polarisable
optically active
rotate the plane of polarized light.
What does the symmetry symbol Sn mean?
rotation-reflection on an improper rotation axis n is the reciprocal of the fraction of a turn needed to reflect the molecule in a mirror plane perpendicular to the axis of rotation (σh)
ortho-hydrogen (H2)
same spin High Temp
Covalent Bonding
sharing of electrons instead of transferring. A diatomic molecule is one that consists of 2 atoms bonded together such as atoms like H2, O2, Br2, I2, Cl2. Cl has 7 electrons in the outer shell so if 2 Cl atoms share then each has 8.
Periodic Table Group
similar chemical properties identified by a number which indicates the number of electrons in outer shell eg group 1 = alkali metals which have a single electron in outer shell
Octohedral d¹ to d³ are all __________ configurations and therefore have no low spin
single state
If only one possible configuration is available the configuration should be referred to as
single state configuration
an associative mechanism corresponds to a
sn2 mechanism, the first step is slow and rate determining and a 7 coordinate complex intermediate is formed, an associative mechanism reflects a second order rate law
Tetrahedral orbitals overlap to form sp3 hybridization. What about octahedral orbitals?
sp3d2 hybridization of atomic orbitals has to do with valence bond theory
Excitation is only allowed if the
spin direction of the electron is preserved
Why do we care about d orbital splitting?
splitting represents homo (t2g) -lumo (eg*) gap, thus determines chemistry of substance ur losing electron density in homo and gaining in lumo etc so Δo determines relative stability of coord compound (smaller Δo = more labile or more prone to exchange w/external molecules)
d⁸ metal centers often have __________ geometry
square planar
associative mechanisms are more common for
square planar d8 complexes eg Au(III), Pt(II), Pd(II) and Ir(II)
what is the geometry of the anticancer drug cisplatin
square planar with a metal center being Pt(II)
Draw the orbital diagram for [Ni(OH2)6]Cl2 and give the crystal field stabilisation energy
stabilisation energy = 2(0.6) + 6(-0.4) = -1.2
If the complex is a cation (⁺), then the metal __________
stays the same
What is a stereoisomer?
stereo or configurational isomers are made up same atoms AND each atom bonded to same atoms, but are arranged differently fyi: 2 types are enantiomers (mirror images) and diastereomers (not mirror images e.g. cis/trans)
The greater the overlap between two orbitals the
stronger the bond
Orbital
subshells s, p, d, f general regions of space around an atom where electrons of a specific energy level are found. They describe movement of e- over time; appear as a cloud and form shapes. S- spherical P-dumbbell: 3 different p orbitals: each orbital can only hold 2e-, linear combination of atomic orbitals
Oxidizing Agent
substance that causes an oxidation by taking electrons; an oxidizing agent becomes reduced (more negative).
How do ions effect the total electrons around the central atom when working out a shape of a molecule?
subtract electron for +ve add for -ve
Shell
successive layers of electrons at increasing distances from the nucleus
borderline acids often occur as --- in nature
sulphides
Auranofin is a drug used to treat rheumatoid arthritis, what is the central metal of the complex and provide its geometry
the drug has a linear geometry and contains Au(I)
polarizability can be defined as
the ease with which the electron cloud of an atom or ion can be distorted
Effect on particular orbitals depends on
the geometry of the complex
the chelate effect refers to
the increased stability of a complex containing chelate rings compared to the stability of a similar system containing only monodentate rings, the chelate effect is entropic in origin
why is there little energy penalty for macrocyclic ligands binding to a metal center
the ligands are already covalently constrained to their cyclic form
A high spin complex is one in which the d electrons are arranged to give
the maximum number of unpaired electrons
when looking at reduction potentials, the more positive the value of E
the more spontaneous the reaction
The coordination number of a complex is
the number of donor atoms coordinated to the metal center
fractional coordinates
the position of an atom in a unit cell (x,y,z) 0<x,y,z>1
cis and trans isomers are possible for square planar complexes because
the two identical ligands can be arranged at either 90° or 180° from one another
stable and unstable are ---- terms
thermodynamic
DDTC is used to
tie up excess platinum in the kidneys which has occurred as a result of treatment of cisplatin for cancer
Gram molecular weight or mole
total of mass numbers, or atom weights, of each and every atom in the compound expressed in grams. Remember the number of atoms required to provide gram molecular weight of any element or compound is always avogadro's number, 6.02x10^23
What elements cannot have a full octet?
towards the left-hand side of the periodic table - e.g. Boron
What is measured in uv/vis spec
transmittance, ie the intensity of light transmitted I, relative ot the intensity oif the incident source I0
Crystal Field Theory
treats the ligand ions as simple point charges that interact with the five atomic d orbitals of the central ion. Not ALL ligands are not equal causing separation of ENERGY in d orbital. ELECTRON-ELECTRON REPULSION
What is the most common 5 coordinated geometry
trigonal bipyramidal
Complexes with a coordination number of 5 are
trigonal bipyramidal (dsp³ hybridised, d orbital is dz²) square pyramidal (dsp³ hybridised, d orbital is dx²-y²) Note that the trigonal bipyramidal has a distinguishing length in the z axis which is consistent with occupying the dz² orbital
Complexes with a coordination number of 3 are
trigonal planar (sp² hybridised)
Explain principle of high spin vs low spin. How does this relate to πc and πe?
with high spin, e's occupy higher energy orbitals before pairing in low energy orbital in order to minimize πc (repulsion) and maximize πe (exchange energy)
So for Oh complex, the symmetry of ligands is Ag + Eg + T1u. Check column to far right of character table...what is symmetry of metal d orbitals? What MO formed? What would MO diagram look like? When creating MO diagram for coord complex, using metal as central atom (on left of diagram) and ligands as GO's (right).
x2-y2 is Eg xy, xz, yz are T2g •only Eg forms MO: 2 bonding, 2 antibonding (evidently metal d orbital contributes more to Eg*, bc bonding Eg already occupied by ligand e's) •T2g of d orbital remain nonbonding (but d orbital keeps e's here nevertheless) fyi Ag of ligand hook up with metal 4s...T1u " go with metal 4p
What is the uncertainty in a toy ball (mass = 150g) moving at 50ms-1, with an uncertainty in the velocity of ±0.1ms-1?
Δx=h/4πΔp = 6.626x10^-34 / 4π(150x10^-3 x 2(0.1)) = 1.76x10^-33 m
Heisenberg Uncertainty Principle
ΔxΔp≥h/4π Δx is the uncertainty in position Δp is the uncertainty in momentum *If Δx is reduced Δp will increase* and vice versa
What greek letter used in π systems to designate # of atoms metal center is interacting with?
η (eta) used in hydrocarbon (organic) π systems
Metal bound to ethylene dbl bond would be η_?
η2
What is the de Brogile Relationship?
λ= h/p λ is wavelength (m), h is Planck's constant (J s), p is momentum (mass x velocity) (kg ms-1)
Co(etda) complex forms 5 chelate rings around cobalt atom. λ and Δ cannot be applied to rings that are fused or coplanar. But there are 3 pairs of rings that can name λ or Δ. If pairs are determined to be ΔΔλ, what would enantiomer be?
λλΔ
What greek letter used for bridging ligands (joining two metals)?
μ (mu)
What is the spin-only formula for magnetic moment and give its units?
μeff= √(n(n+2)) Units = μB = Bohr magnetons n is the number of unpaired electrons
Which have larger Δ (ligand field split): π donors or π acceptors?
π acceptors have larger Δ (ligand field split)
Ligands with occupied p orbitals like halides (F-, Cl-, Br-, I-), are potentially π donors or π acceptors? What does this mean for spin config?
π donors (smaller Δ...ligand field split) as result halide complexes tend to have high spin configurations
Do dxy, dxz, and dyz orbitals interact with ligands via σ or π interaction?
π interaction
examples of negatively charged ligands? (shtload)
π system w/negative charge (e.g. cyclopentadienyl or ferrocene) hydride (H-) acetate (-C=O -O-) OH- Cl-/F-/I- cyano (CN-) oxo (O2-) thiocyanate (SCN-)
construct simple MO diag for high spin for d orbital with 5 electrons. what is πc and πe?
πc = 0 πe = 4 Δo → 2..bc 2 electrons jumped remember with low spin there was πc = 2...so cost of jumping Δo ~ same...Δo vs πc neglible...molecule could go high or low spin for d5!
construct simple MO diag for low spin for d orbital with 5 electrons. what is πc and πe?
πc = 2..bc 2 paired πe = 4
carbon monoxide and cyanide are σ ___ and π ____
σ donors and π acceptor
Stronger ligand fields give a higher value of __________
∆₀ and lambda
The field splitting energy is the:
∆₀ difference between lower energy orbitals and higher energy orbitals
What is the magnetic moment for [Fe(CN)6]3-?
√3 μB
What is the magnetic moment for [Fe(OH2)6]3+?
√35μB
What is the magnetic moment for [NiBr4]2-?
√8 μB