Useful equations used throughout the course

Kinetics

Zero Order Reactions Rate = –k [A] = –kt + [A]o t½ = [A]o/2k k is the rate constant in units of mol·L–1s–1

 

First Order Reactions Rate = –k[A] ln[A] = –kt + ln[A]o t½ = 0.693/k k is the rate constant in units of s–1

 

Second Order Reactions Rate = –k[A]2 1/[A] = kt + 1/[A]o t½ = 1/[A]ok k is the rate constant in units of mol–1Ls–1

 

Rate is the reaction velocity in units of mol·L–1s–1

t is time in units of s

[A]o is the initial concentration of the reactant in units of mol·L–1

t½ is the half-life, the time for the initial concentration to decrease by 50%

[A] is the concentration of reactant at any time t

Arrhenius equation

 

 

k is the rate constant, in any appropriate units

Ea is the activation energy in units of J/mol or kJ/mol

R is the gas constant, 8.314 J/mol·K

T is the absolute temperature in units of Kelvins, T(K) = T(oC) + 273.15

A is the pre-exponential factor in the same units as the rate constant

Equilibrium

Quadratic equation

 

Kp - Kc relationship

 

Kp is the equilibrium constant written in terms of partial pressures (atm)

Kc is the equilibrium constant written in terms of concentrations (M)

R is the gas constant, = 0.0821 L·atm/mol·K

T is the absolute temperature in units of Kelvins, T(K) = T(oC) + 273.15

Δn is the change in moles of gas phase materials

Law of Multiple Equilibria: When chemical equations are added, equilbrium constants are multiplied

Reaction 1: A(aq) + B(aq) C(aq) + D(aq)Kc1

Reaction 2: C(aq) + E(aq) F(aq) + B(aq)Kc2

Net reaction: A(aq) + E(aq) D(aq) + F(aq)Kcnet = Kc1×Kc2

Acid - Base Chemistry

definition of pH pH = –log[H3O+]

 

[H3O+] is the hydronium ion concentration in units of M

definition of pOH pH = –log[OH]

 

[OH] is the hydroxide ion concentration in units of M

definition of pKa pKa = –logKa

 

Ka is the acid ionization equilibrium constant

definition of % ionization

 

α is the % ionization

[H3O+]e is the equilibrium concentration of hydronium ion in units of M

[A]e is the equilibrium concentration of the conjugate base anion in units of M

[HA]init is the initial concentration of the weak acid in units of M

Ka - Kb relationship Kw = KaKb for conjugate acid/base pairs

 

Kw is the equilibrium constant for the autoionization of water

Ka is the acid ionization equilibrium constant

Kb is the base ionization equilibrium constant

Kc for acid-base reactions Kc = KaKb/Kw

 

Kw is the equilibrium constant for the autoionization of water

Ka is the acid ionization equilibrium constant

Kb is the base ionization equilibrium constant

Thermodynamics

First Law ΔU = q + w

 

ΔU is the internal energy in units of J/mol or kJ/mol

q Is the heat transferred in units of J/mol or kJ/mol

w is the work in units of J/mol or kJ/mol

Pressure-volume work w = –PΔV

 

w is the work in units of L-atm

P is the constant external pressure in units of atm

ΔV is the volume change in units of L

Enthalpy of reaction

 

 

ΔHo is the enthalpy of reaction in units of kJ

ΔHof is the enthalpy of formation in units of kJ/mol

mi is the stoichiometric coefficient for each product

mj is the stoichiometric coefficient for each reactant

Entropy of reaction

 

 

ΔSo is the entropy of reaction in units of J/K

So is the absolute entropy in units of J/mol·K

mi is the stoichiometric coefficient for each product

mj is the stoichiometric coefficient for each reactant

Second Law for a spontaneous process

 

ΔS is the change in entropy in units of J/mol·K

T is the absolute temperature in units of Kelvins, T(K) = T(oC) + 273.15

Third Law S = RlnW

 

S is the absolute entropy in units of J/mol·K

R is the gas constant, 8.314 J/mol·K

W is the degeneracy of the system (unitless)

Trouton's equation

 

 

ΔSovap is the entropy change for vaporization in units of J/K

ΔHovap is the enthalpy change for vaporization in units of J

Tbp is the boiling point in units of Kelvins, T(K) = T(oC) + 273.15)

Gibb's Free Energy ΔG = ΔH – TΔS

 

ΔG is the Gibb's Free Energy change in units of kJ

ΔH is the enthalpy change in units of kJ

ΔS is the entropy change in units of kJ/K

Tbp is the boiling point in units of Kelvins, T(K) = T(oC) + 273.15)

ΔG - w relationship ΔG = wmax

 

ΔG is the Gibb's Free Energy change in units of kJ

wmax is the maximum work available from a system in units of kJ

ΔG at nonstandard conditions ΔG = ΔGo + RTlnQ

 

ΔG is the Gibb's Free Energy change in units of kJ

ΔGo is the Gibb's Free Energy change at standard conditions in units of kJ

R is the gas constant, 8.314 J/mol·K

T is the absolute temperature in units of Kelvins, T(K) = T(oC) + 273.15

Q is the reaction quotient expressed with gases in units of atm and concentration in units of M

ΔG - Keq relationship ΔGo =–RTln Keq

 

ΔGo is the Gibb's Free Energy change at standard conditions in units of kJ

R is the gas constant, 8.314 J/mol·K

T is the absolute temperature in units of Kelvins, T(K) = T(oC) + 273.15

Keq is the thermodynamic equilibrium constant expressed with gases in units of atm and concentration in units of M

van't Hoff equation

 

 

Keq is the thermodynamic equilibrium constant expressed with gases in units of atm and concentration in units of M

R is the gas constant, 8.314 J/mol·K

T is the absolute temperature in units of Kelvins, T(K) = T(oC) + 273.15

ΔHo is the enthalpy change at standard conditions in units of J

ΔSo is the entropy change at standard conditions in units of J/K

Electrochemistry

Standard cell potential Eocell = Eored + Eoox

 

Eocell is the standard cell potential in units of V

Eored is the potential for the reduction half-reaction in units of V

Eoox is the potential for the oxidation half-reaction in units of V

Nernst Equation

 

 

Ecell is the cell potential in units of V

Eocell is the standard cell potential in units of V

R is the gas constant, 8.314 J/mol·K

T is the absolute temperature in units of Kelvins, T(K) = T(oC) + 273.15

n is the number of electrons transferred in the balanced chemical equation

F is Faraday's constant, 96485 C/mol

Q is the reaction quotient expressed with gases in units of atm and concentration in units of M

Eo - Keq relationship

 

 

Eocell is the standard cell potential in units of V

R is the gas constant, 8.314 J/mol·K

T is the absolute temperature in units of Kelvins, T(K) = T(oC) + 273.15

n is the number of electrons transferred in the balanced chemical equation

F is Faraday's constant, 96485 C/mol

Keq is the reaction quotient expressed with gases in units of atm and concentration in units of M

Eo - ΔGo relationship ΔGo =–nFEocell

 

Eocell is the standard cell potential in units of V

ΔGo is the Gibb's Free Energy change at standard conditions in units of J

n is the number of electrons transferred in the balanced chemical equation

F is Faraday's constant, 96485 C/mol

Eo - w relationship wmax = –nFEcell

 

Eocell is the standard cell potential in units of V

wmax is the maximum work available from a system in units of J

n is the number of electrons transferred in the balanced chemical equation

F is Faraday's constant, 96485 C/mol

Electrolysis nF = At

 

A is the current passed in units of amps

t is the time in units of s

n is the number of electrons transferred in the balanced chemical equation

F is Faraday's constant, 96485 C/mol