powerful carbon-carbon bond-forming chemical reaction discovered by Rainer Ludwig Claisen. The heating of an allyl vinyl ether will initiate a [3,3]-sigmatropic rearrangement to give a γ,δ-unsaturated carbonyl.

[image]

a means of calculating the lattice energy of a crystalline ionic compound. In 1918^[1] Max Born and Alfred Landé proposed that the lattice energy could be derived from the electrostatic potential of the ionic lattice and a repulsive potential energy term.^[2]

[image] (Joules/mol)

where

[image] = Avogadros number

[image] = Madelung constant, relating to the geometry of the crystal.

[image] = charge of cation in electron units

[image] = charge of anion in electron units

[image] = electron charge in coulombs, 1.6022 × 10⁻¹⁹ C

[image] = permittivity of free space

[image] = 1.112 × 10⁻¹⁰ C²/(J m)

[image] = distance to closest ion in meters

[image] = Born exponent, a number between 5 and 12, determined experimentally by measuring the compressibility of the solid, or derived theoretically.

Le Chatelier's Principle

3 Factors that Perturb Equilibrium

1) Change in Concentration of reactants or products

2)Change in Pressure

 Adding an inert gas into a gas-phase equilibrium at constant volume does not result in a shift. This is because the addition of a non-reactive gas does not change the partial pressures of the other gases in the container. While it is true that the total pressure of the system increases, the total pressure does not have any effect on the equilibrium constant; rather, it is a change in partial pressures that will cause a shift in the equilibrium. If, however, the volume is allowed to increase in the process, the partial pressures of all gases would be decreased resulting in a shift towards the side with the greater number of moles of gas

3) Change in Termperature

HCl-hydrochloric acid

HBr-Hydrobromic Acid

HI-Hydroiodic Acid

HNO₃-Nitric Acid

H₂SO₄-Sulfuric Acid

HClO₄-Perchloric Acid

[image]

and

[image]

H

CH₃

CH2CH3

CN 

OH

Cl

NO

[image]

The Total Energy of a System and its surroundings is always constant

U=Q-W

H = U + PV

for constant pressure (atmospheric conditions)

ΔH = ΔU + PΔV

C_v = (dU/dT)

C_p=(dH/dT)

Cp-Cv = R

G = H-TS (usually constant pressure)

A = U - TS (usually constant volume)

F=C-P+2

F = degrees of freedom

C=components

P=phases

the vapor pressure of an ideal solution is dependent on the vapor pressure of each chemical component and the mole fraction of the component present in the solution.

Once the components in the solution have reached equilibrium, the total vapor pressure p of the solution is:

[image]

and the individual vapor pressure for each component is

[image]

where

p*_i is the vapor pressure of the pure component

x_i is the mole fraction of the component in solution

U (stat mech)

P

S

[image]

or

[image]

where:

ΔP is the pressure drop

L is the length of pipe

μ is the dynamic viscosity

Q is the volumetric flow rate

r is the radius

d is the diameter

d[A]/dt = -k [A]

[A] = [A]₀ exp(-k t)

ln([A]) = ln([A]₀) - k t

d[A]/dt = -k [A]² or dx/dt = -k [A][B]

1/[A] - 1/[A]₀ = k t  or

(1/(a-b)) [ln((a-x)/(b-x))-ln(a/b)] = k t  

1/[A] = 1/[A]₀ + k t

1) minimize Q (solute concentration) by adding slowly

2) maximize S (precipitate solubility) by doing at higher temperatures

At a constant temperature, the amount of a given gas dissolved in a given type and volume of liquid is directly proportional to the partial pressure of that gas in equilibrium with that liquid.

FOR DILUTE SOLUTIONS!!

Potentiometry-measure EMF compared to standard zero current. either uses electrodes (like pH meters) to directly measure ion activity, or uses electrodes to find end points of titrations

Voltammetry-electrolysis is carreid out so the analyte is completely oxidized/reduced to a product of known composition. requires application of current through the whole process

Maxwell Equations

Internal Energy (U)

Maxwell Equations

Gibbs Free Energy (G)

Maxwell Equations

Helmholtz Energy (A)

Maxwell Relations

[image]

[image]

Kinetic Theory

Temperature and Velocity

The Cope rearrangement is an extensively studied organic reaction involving the [3,3]-sigmatropic rearrangement of 1,5-dienes. It was developed byArthur C. Cope. For example 3-methyl-1,5-hexadiene heated to 300°C yields 1,5-heptadiene.

[image]

The McLafferty rearrangement is a reaction observed in mass spectrometry. It is sometimes found that a molecule containing a keto-group undergoes β-cleavage, with the gain of the γ-hydrogen atom. This rearrangement may take place by a radical or ionic mechanism

[image]

The Hofmann rearrangement is the organic reaction of a primary amide to a primary amine with one fewer carbon atom

[image]

Lucas' reagent is a solution of zinc chloride in concentrated hydrochloric acid, used to classify alcohols of low molecular weight.

[image]

Temperature 

T(Rankine) = T(F) + 460

The Van Deemter equation in chromatography relates the variance per unit length of a separation column to the linear mobile phase velocity by considering physical, kinetic, and thermodynamic properties of a separation.[1] These properties include pathways within the column, diffusion (axial and longitudinal), and mass transfer kinetics between stationary and mobile phases.

[image]

Where

• A = Eddy-diffusion
• B = Longitudinal diffusion
• C = mass transfer kinetics of the analyte between mobile and stationary phase
• u = Linear Velocity.

he existence of co-ordination compounds that have the same composition differing with the connectivity of the metal to a ligand.

[image]

Electronic: can't do s-s p-p d-d etc. 

Rotational-must differ by +-1

an unsaturated compound derived by the reaction of an aldehyde or ketone with a secondary amine followed by loss of H2O

[image]

is a functional group or chemical compound containing a carbon–nitrogen double bond [1]. Due to their diverse reactivity, imines are common substrates in a wide variety of transformations. An imine can be synthesised by the nucleophilic addition of an amine to a ketone or aldehyde giving a hemiaminal -C(OH)(NHR)- followed by an elimination of water to yield the imine

[image]

Rotational and Vibrational

For the spontaneous Raman effect, the molecule will be excited from the ground state to a virtual energy state, and relax into a vibrational excited state. Two series of lines exist around this central vibrational transition. They correspond to the complimentary rotational transition. Anti-Stokes lines correspond to rotational relaxation whereas Stokes lines correspond to rotational excitation.