Physical Chemistry with Formulas and Examples

Ihsan Basaran

July 4, 2014

Abstract
It is a document includes most common formulas of Physical Chem-
istry

1 Thermodynamic
1.1 First Law
1.1.1 General expressin of Internal Energy
∆U = q + w (1)
Where U is internal energy, q is heat, and w is work

1.1.2 General expression of Work

W = Pex .∆V (2)
Where W is work, Pex is external pressure, ∆V is change in the volume

1.1.3 Work at reversible processes

V2
W = −RT ln (3)
V1
Where V2 is final volume and V1 is the volume at the begining of process

1.1.4 Heat capacity at constant volume : Cv

 δU 
Cv = (4)
δT V

∆U = n.Cv .∆T (5)

Qv = n.Cv .∆T (6)

Also Qv = ∆ U

1.1.5 Heat capacity at constant pressure : Cp

 δU 
Cp = (7)
δT p

∆U = n.Cp .∆T (8)

Qp = n.Cp .∆T (9)

Cp = Cv + R (10)

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 • for an unimolecular atom ; Cv = 3/2 R and Cp = 5/2 R
• for an bimolecular atom ; Cv = 5/2 R and Cp = 7/2 R
• for an multimolecular atom ; Cv = 7/2 R and Cp = 9/2 R

2 Phase Diagrams and Chemical Potential

2.1 General formula for chemical potential
dG = (µ1 − µ2 )dn (11)
µ1 : chemical potential at point 1
µ2 : chemical potential at point 2
dG : Gibbs Energy

2.2 The dependence of stability on conditions

2.2.1 Temperature
   
δG δµ
= −Sm −→ = −Sm (12)
δT p δT p
−Sm : molar entropy

2.2.2 Pressure
 
δµ
= Vm −→ ∆µ = Vm P (13)
δp T
Vm : molar volume

2.3 Effect of pressure on vapour pressure

ln p Vm
= × ∆P (14)
p ∗ RT

2.4 Clepeyron Equations for Phase Boundaries

Slope of the diagrams are determined via Clepeyron equations
dp ∆trs S
= (15)
dT ∆trs V
∆trs S : entropy change for transferred substance
∆trs V : Volume of transferred substance

2.4.1 Solid-Liqud Phase Boundary

dp ∆m H
= (16)
dT T ∆m V
∆m H : enthalpy change for melting
∆m V : Volume change while melting

2
2.4.2 Liquid-Gas Boundary
dp ∆vap H
= (17)
dT T ∆vap V
∆V g ≫ ∆V liq →
∆V vap = ∆V g
V = RT/P →
dp ∆vap H
= (18)
dT T (RT /P )

2.4.3 Finding the vapour pressure of a liquid at desired temperature

−
γ
p = p∗e (19)
and
∆H vap 1 1
γ= × ( ) − ( ∗) (20)
R T T

3 Simple Mixtures
3.1 Partial molar quantities
3.1.1 Partial molar volume
For a substance J, molar volume in a solution is
 δV 
Vj = (21)
nj p,t,n′
In a mixture including liquid a,b

V = Va na + Vb nb (22)

3.1.2 Partial Molar Gibbs energy

G = n a µA + n b µB (23)

3.1.3 Other important equations for chemical potential

U = −pV +T S+G −→ dU = −pdV +T ds+dG = −pdV +T ds+µdna +µdnb +..
(24)
When the volume and entropy are constant

dU = µdna + µdnb + ....... (25)

3.1.4 Gibbs-Duhem equation

In a two componnent mixture, the chemical potential of one substance can’t
change independently without the other substance’s chemical potemtial.
nA
dµB = − dµA (26)
nB

3.2 Termodynamics of mixtures

 
δGmix = −nRT xa lnxA + xB lnxB (27)

 δGmix   
∆S mix = = −nR xa lnxA + xB lnxB (28)
δT

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3.3 Chemical potentials of Liquids
pA
µA = µA∗ − RT ln (29)
pA ∗
µA∗ : chemical potential of pure liquid A
pA ∗ : vapour pressure of pure liquid A

3.4 Ideal solutions

3.4.1 Rault’s law
pA = xA × pA ∗ (30)

µA = µA ∗ + RT lnxa (31)
pA ∗ : vapour pressure of pure liquid A
xA : mole fraction of liquid A in the solution
µA ∗ : chemical potential of pure liquid A

3.4.2 Ideal dilute sulutions and Henry’s law

pB = xB KB (32)
KB : extrapolated Henry pressure

4 Properties of Solutions
4.1 Liquid mixtures
4.1.1 Ideal solutions
for an Ideal solution ;

∆H mix = ∆Gmix + T ∆S mix = 0 (33)

∆V mix = 0, ∆Hmix = 0 (34)

4.1.2 Regular solutions

in regular solutions ;
∆H = 0 and
∆S = 0

H E = nβRT xA xb (35)
E
H :exceeded entalphy
β :is a function for molecular interactions

∆Gmix = nRT (xA ln xA + xB ln xB + βxA xB ) (36)

4.2 Collugative preperties

Chemical potential change when a solute introduced to a liquid

µ∗ = µ∗ + RT ln xA (37)

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 4.2.1 Increasing of boiling point
∆H vap  1 1
xB = − (38)
R T ∗ T
T ∗ : normal boiling point

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