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KEY EQUATIONS
1. General 4. Equilibrium and electrochemistry
Roots of the equation ax2 ⫹ bx ⫹ c ⫽ 0: Definition of activity (for ideal systems):
⫺ b ⫾ 2b2 ⫺ 4ac For an ideal gas: aJ ⫽ PJ 兾 P⬚, P⬚ ⫽ 1 bar
x⫽
2a For a solute in an ideal solution: aJ ⫽ [J]兾 c⬚, c⬚ ⫽ 1 molⴢL−1
Kinetic energy of a particle of mass m and speed v: For a pure liquid or solid: aJ ⫽ 1
1 Reaction quotient and equilibrium constant:
Ek ⫽ mv2
2 For the reaction a A ⫹ b B ¡ c C ⫹ d D, Q ⫽ aCcaDd 兾 aAaaBb
Gravitational potential energy of a body of mass m at height h:
For the equilibrium a A ⫹ b B Δ c C ⫹ d D
Ep ⫽ mgh
K ⫽ (aCcaDd 兾 aAaaBb) equilibrium
Coulomb potential energy of two charges Q1 and Q2 at a separation r:
Variation of Gibbs free energy of reaction with composition:
Ep ⫽ Q1Q2兾4␲e0r
¢Gr ⫽ ¢Gr⬚ ⫹ RT ln Q
2. Structure and spectroscopy
Relation between standard reaction Gibbs free energy and equilibrium
Relation between the wavelength, ␭, and frequency, v, of electromagnetic
constant:
radiation:
␭v ⫽ c ¢Gr⬚ ⫽ ⫺RT ln K
Energy of a photon of electromagnetic radiation of frequency v: van ’t Hoff equation:
E ⫽ hv K2 ¢Hr⬚ 1 1
ln ⫽ a ⫺ b
de Broglie relation: K1 R T1 T2
␭ ⫽ h兾p Relation between K and Kc:
Heisenberg uncertainty principle:
K ⫽ 1c⬚RT兾P⬚2 ¢n r Kc   P⬚兾Rc⬚ ⫽ 12.03 K
1
¢p¢x ⱖ h Clausius–Clapeyron equation:
2
P2 ¢Hvap⬚ 1 1
Energy of a particle of mass m in a one-dimensional box of length L: ln ⫽ a ⫺ b
En ⫽ n2h2兾8mL2, n ⫽ 1, 2, . . . P1 R T1 T2
Bohr frequency condition: Relation between Gibbs free energy and maximum nonexpansion work:
hv ⫽ Eupper ⫺ Elower ¢G ⫽ we,max at constant temperature and pressure
Energy levels of a hydrogenlike atom of atomic number Z: Relation between pH and pOH:
En ⫽ ⫺Z2hR 兾n2, n ⫽ 1, 2, . . .
pH ⫹ pOH ⫽ pKw
Formal charge:
1 Relation between acidity and basicity constants of a conjugate acid–base pair:
FC ⫽ V ⫺ aL ⫹ Sb pKa ⫹ pKb ⫽ pKw
2
3. Thermodynamics Henderson–Hasselbalch equation:
Ideal gas law: pH ⫽ pKa ⫹ log1[base] initial兾[acid] initial 2
PV ⫽ nRT Relation between the Gibbs free energy of reaction and the cell potential:
Expansion work against constant external pressure: ¢G ⫽ ⫺nFEcell
w ⫽ ⫺Pex ¢V Relation between the equilibrium constant for a cell reaction and the stan-
Work of reversible, isothermal expansion of an ideal gas: dard cell potential:
w ⫽ ⫺nRT ln1Vfinal兾Vinitial 2 ln K ⫽ nrFEcell⬚兾RT
First law of thermodynamics: Nernst equation:
¢U ⫹ q ⫹ w Ecell ⫽ Ecell⬚ ⫺ 1RT兾nrF2 ln Q
Definition of entropy change:
¢S ⫽ qrev兾T
5. Kinetics
Average reaction rate:
Definition of enthalpy:
H ⫽ U ⫹ PV Rate of consumption of R ⫽ ⫺
¢[R]
Definition of Gibbs free energy: ¢t
G ⫽ H ⫺ TS ¢[P]
Rate of formation of P ⫽
Change in Gibbs free energy at constant temperature: ¢t
¢G ⫽ ¢H ⫺ T¢S Unique average rate for a A ⫹ b B ¡ c C ⫹ d D:
Relation between the constant-pressure and constant-volume molar heat
1 ¢[A] 1 ¢[B] 1 ¢[C] 1 ¢[D]
capacities of an ideal gas: Unique average reaction rate ⫽⫺ ⫽⫺ ⫽ ⫽
CP, m ⫽ CV, m ⫹ R a ¢t b ¢t c ¢t d ¢t
Integrated rate laws:
Standard reaction enthalpy (X ⫽ H) and Gibbs free energy (X ⫽ G) from
For rate of disappearance of A ⫽ k[A],
standard enthalpies and Gibbs free energies of formation:
[A] r
¢X⬚ ⫽ g n¢Xf⬚1products2 ⫺ g n¢Xf⬚1reactants2, n in moles ln ⫽ ⫺kt     [A] t ⫽ [A] 0e ⫺kt
[A] 0
¢Xr⬚ ⫽ g nr ¢Xf⬚1products2 ⫺ g nr ¢Xf⬚1reactants2, nr a pure number
Standard reaction entropy: For rate of disappearance of A ⫽ k[A]2,
¢S⬚ ⫽ g nSm⬚1products2 ⫺ g nSm⬚1reactants2, n in moles 1 1 [A] 0 1 1
⫺ ⫽ kt     [A] t ⫽    ⫽ kt ⫹
Kirchhoff’s law: [A] t [A] 0 1 ⫹ [A] 0kt [A] t [A] 0
¢H2⬚ ⫽ ¢H1⬚ ⫹ ¢CP 1T2 ⫺ T1 2
Half-life of a reactant in a first-order reaction:
Change in entropy when a substance of constant heat capacity, C, is heated
t1兾2 ⫽ 1ln 22兾k
from T1 to T2:
¢S ⫽ C ln1T2兾T1 2 Arrhenius equation:
Change in entropy when an ideal gas expands isothermally from V1 to V2: ln ⫽ ln A ⫺ Ea兾RT
¢S ⫽ nR ln1V2兾V1 2 The rate constant at one temperature in terms of its value at another
temperature:
Boltzmann’s formula for the statistical entropy:
k2 Ea 1 1
S ⫽ k ln W ln ⫽ a ⫺ b
k1 R T1 T2
Entropy change of the surroundings for a process in a system with enthalpy
change ⌬H: The equilibrium constant in terms of the rate constants:
¢Ssurr ⫽ ⫺¢H兾T K ⫽ kforward 兾kreverse