Table 1.

10 (continued)
Λ0m ¼ ν+ _ λ+ + ν‐ _ λ‐ Law of the independent migration of ions
The limiting molar conductivity is comprised of the
two independent limiting molar conductivities of the
anions and cations.
Transport
F ¼ _R _ T
c
_ δc
δx
__
p,T
Thermodynamic force
A concentration gradient establishes a thermodynamic
force F.
J ¼ _D _ dIN
dx
Fick’s first law of diffusion
Flux of matter is defined by the concentration gradient
along x; IN ¼ N
V
is the molecule density; D is the
diffusion coefficient.
J ¼ _κ _ dT
dx
Thermal conduction
Flux of energy along a temperature gradient; κ is the
thermal conductivity.
J ¼ _η _ dvx
dx
Flux of momentum
When molecules switch from one flow layer to
another, their momentum is also migrating; η is the
viscosity.
Kinetics
k ¼ A _ e_Ea
R_T Arrhenius equation

The rate constants of most reactions depend on the

temperature.
dlnk
dT
__
¼ Ea
R _ T2
The generalised dependency of rate constants on
temperature, which applies to all reactions irrespective
of their adhering to the Arrhenius relation or not.
v ¼ vmax _ c0ðSÞ
c0ðSÞ þ Km
Michaelis-Menten enzyme kinetics
Surface adsorption
Γ¼K_p
K_pþ1
Langmuir adsorption isotherm without dissociation
The Langmuir constant K is the ratio of the rate
constants for adsorption and desorption: K ¼ kads
kdes
.
Γ¼
ffiffiffiffiffiffiffiffiffiffi
K_p
p
ffiffiffiffiffiffiffiffiffiffi
K_p
p
þ1
Langmuir adsorption isotherm with dissociation into
two species
Table 1.11 Kinetic rate laws in their differential and integrated forms, and the derived half lives
Order Differential form Integrated form Half life
0_1
νA
_ dcðAÞ
dt
¼k
c(A)¼ _νA _ k _ t + c0(A)
t1=2 ¼ c0ðAÞ
2_k
1_1
νA
_ dcðAÞ
dt
¼ k _ cðAÞ
_ ln c(A) ¼ νA _ k _ t _ ln c0(A)
t1=2 ¼ ln 2
k
2_1
νA
_ dcðAÞ
dt
¼ k _ cðAÞ2
1
cðAÞ ¼ νA _ k_tþ1
c0ðAÞ t1=2 ¼ 1
k _ c0ðAÞ
3_1
νA
_ dcðAÞ
dt
¼ k _ cðAÞ3
1
cðAÞ2 ¼ 2 _ νA _ k _ t þ 1
c0ðAÞ2 t1=2 ¼3
2 _ k _ c0ðAÞ2
Table 1.12 Interactions between molecules. α: polarisability; ε0: vacuum permittivity; I: first
ionisation potential; μ: dipole moment; r: distance between the two atoms/molecules
Interaction Potential energy Explanation
Order of
magnitude
(kJ mol_1)
Covalent
bond
|V| ¼ 200–800
Coulomb
interaction V ¼ _zA _ zB _ e2
4π _ ε0 _ r
Interaction between two
ions
|V| ¼ 40–400
Ion-dipole
interaction
V¼_z_e_μ
4π _ ε0 _ r2
Interaction between ion and
permanent dipole
|V| ¼ 4–40
Keesom
interaction V ¼ _2
3
_ μ2
A
_ μ2
B
4π _ ε0 ð Þ2 _ r6
_1
k_T
Interaction between two
permanent dipoles
|V| ¼ 0.4–4
Ion-induced
dipole
interaction
V ¼ _1
2
_ α _ e2
4π _ ε0 _ r4
Interaction between ion and
induced dipole
|V| ¼ 0.4–4
Debye force
V ¼ _ α _ μ2
4π _ ε0 ð Þ2 _ r6
Interaction between
permanent dipole and
induced dipole
|V| ¼ 0.4–4
London
dispersion
force
V ¼ _3
4
_ I _ α2
r6
(pure substance)
Interaction between
temporary dipole and
induced dipole
|V| < 0.4
V ¼ _3
2
_ IA _ IB
IA þ IB
_ αA _ αB
r6
(mixture of A and B)
|V| < 0.4
Hydrogen
bond
|V| ¼ 4–40