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Physical Chemistry with Formulas and Examples

Technical Report · August 2014


DOI: 10.13140/2.1.1984.5442

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İhsan Basaran
Çanakkale Onsekiz Mart Üniversitesi
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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
ΔU = q + w (1)
Where U is internal energy, q is heat, and w is work

1.1.2 General expression of Work


W = Pex .ΔV (2)
Where W is work, Pex is external pressure, ΔV 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

ΔU = n.Cv .ΔT (5)

Qv = n.Cv .ΔT (6)


Also Qv = Δ U

1.1.5 Heat capacity at constant pressure : Cp


 δU 
Cp = (7)
δT p

ΔU = n.Cp .ΔT (8)

Qp = n.Cp .ΔT (9)

Cp = Cv + R (10)

1
• 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 −→ Δμ = Vm P (13)
δp T
Vm : molar volume

2.3 Effect of pressure on vapour pressure


ln p Vm

= × ΔP (14)
p RT

2.4 Clepeyron Equations for Phase Boundaries


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

2.4.1 Solid-Liqud Phase Boundary


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

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

2.4.3 Finding the vapour pressure of a liquid at desired temperature



p = p∗e γ
(19)
and
ΔH 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   
ΔS mix = = −nR xa lnxA + xB lnxB (28)
δT

3
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 ;

ΔH mix = ΔGmix + T ΔS mix = 0 (33)

ΔV mix = 0, ΔHmix = 0 (34)

4.1.2 Regular solutions


in regular solutions ;
ΔH = 0 and
ΔS = 0

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

ΔGmix = 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)

4
4.2.1 Increasing of boiling point
ΔH vap  1 1
xB = ∗
− (38)
R T T
T ∗ : normal boiling point

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