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net/publication/271205243

DOI: 10.13140/2.1.1984.5442

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İhsan Basaran

Çanakkale Onsekiz Mart Üniversitesi

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All content following this page was uploaded by İhsan Basaran on 22 January 2015.

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

W = Pex .ΔV (2)

Where W is work, Pex is external pressure, ΔV is change in the volume

V2

W = −RT ln (3)

V1

Where V2 is ﬁnal volume and V1 is the volume at the begining of process

δU

Cv = (4)

δT V

Also Qv = Δ U

δU

Cp = (7)

δT p

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

2.1 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

2.2.1 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

ln p Vm

∗

= × ΔP (14)

p RT

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

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 )

−

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)

G = n a μA + n b μB (23)

U = −pV +T S+G −→ dU = −pdV +T ds+dG = −pdV +T ds+μdna +μdnb +..

(24)

When the volume and entropy are constant

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

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

3.4.1 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

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 ;

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

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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