CHAPTER 1: THERMODYNAMICS

Chapter 1 - Content
1.2 Thermodynamics
1.2.1. Mole
1.3 Ideal Gases
1.4 Real Gases

1.2 Thermodynamics
Termo Heat, Dynamic Change
Thermodynamic is science of knowledge focusing on macroscopic
system as a result of the change of temperature
A study involving equilibrium properties of a system and
changes in equilibrium properties while the process is taking
place.
Thermodynamic system
1. Open transfer of matter/energy between system & surrounding
2. Close no transfer of matter between the two.
3. Isolated no transfer of matter & energy between the two.
surrounding
system
wall
2

1.2 Thermodynamic (continue ..)

The wall is divided into 2 types:
a. Permeable adiabatic (const. temp. due to no transfer of heat)
b. Impermeable nonadiabatic (temp. changes & transfer of heat)
Equilibrium
No macroscopic change in properties with time
a. Mechanical (force) no acceleration, no turbulent
b. Material no change, no chemical reaction
c. Thermal no change in temperature/heat
Thermodynamic properties
Intensive
Extensive
a. Composition/conc.
(independent of matter)
a. Mass (m)
b. Volume
b. Volume (V) a. Density, (m/V)
c. Pressure
c. Force (F)
b. Pressure, P (F/A)
3

1.2 Thermodynamic (continue ..)

State function
If there is a change in pressure such that,

dP =P2 P1

and/or that its cyclic path = 0,

dP = 0
which is not affected by the path of a process, then pressure
is said to be the state function of the process.

1.2 Thermodynamic (continue ..)

A method to determine whether a thermodynamic property is a
state function or not is by use of Eulers technique.
If, fxy = fyx
Then, the thermodynamic property is said to be the state
function.
Take the function V(T,P) = 3TP3+8T2P4 as an example,
fy = 9xy2+32x2y3
fyx = 9y2+ 64xy3
fx = 3y3+16xy4
fxy = 9y2+ 64xy3
Therefore, V is a state function. Other examples of state functions
include U, H, S and G.
Heat, q, and P-V work, w, is not a state function since its value
depends on the path of the process.
5

1.2.1 Mol, n
Mass having elementary entity equivalent to Avagadro number
NA = 6.021023. Molar mass/molecular weight, M = m/n (g/mol)
where m is mass of substance and n is the number of moles.
1.3 Ideal gases
Equation of state (EoS), resulted from Boyle (PV = k)
& Charles (V T) laws
PV = nRT = mRT/M
P = RT/M

1.3 Ideal gases (Continue ..)

1 V m
V

=
T P , n V m T P
1 V
1 V m
Isothermal compression, (T , P )

=
V P T , n
V m P T

1
Thermal expansion coefficient, (T , P )
V

RT Vm
,
PVm = RT , Vm =
= R/P
P T
1 V
1 R
(T , P ) m = = 1 / T
Vm T P Vm P

Vm
= RT / P 2
P
1 Vm
1 RT
(T , P )
= 2 = 1/ P
Vm P T
Vm P
7

1.4 Real gases

2

a 1 b

+ + ..
Z = 1 + b

RT Vm Vm

-50C
2.00

0C

100C

1.80
300C
1.60
Z
1.40
1.20
1.00
0.80
0

200

400

600

800

1000

P (bar)
8

1.4 Real gases (Continue ..)

Van der Waals equation:

P + a
2

Vm

(Vm b ) = RT

Van der Waals constants:

2

27 R Tc
a=
64 Pc
RTc
b=
8 Pc

1.4 Real gases (Continue ..)

Van der Waals constants:
Gas

a (L2bar.mol-2) b (L.mol-1)

Gas

a (L2bar.mol-2)

b (L.mol-1)

H2

0.2476

0.02661

CH4

2.283

0.04278

He

0.03457

0.02370

C 2H 6

5.562

0.06380

N2

1.408

0.03913

C 3H 8

8.779

0.08445

O2

1.378

0.03183

C4H10 (n)

14.66

0.1226

Cl2

6.579

0.05622

C4H10 (iso)

13.04

0.1142

NO

1.358

0.02789

C5H12 (n)

19.26

0.1460

NO2

5.354

0.04424

CO

1.505

0.03985

H 2O

5.536

0.03049

CO2

3.640

0.04267

10

1.4 Real gases (Continue ..)

Critical constants:
Gas

Tc (K)

Pc (bar)

Gas

Tc (K)

Pc (bar)

H2

33.2

13.0

CH4

190.6

46.0

He-4

5.2

2.27

C2H6

305.4

48.9

N2

126.2

34.0

C 3H 8

369.8

42.5

O2

154.6

50.5

C4H10 (n)

425.2

38.0

Cl2

417

77.0

C4H10 (iso)

408.1

36.5

Bromin

584

103.0

Ethylena

282.4

50.4

Ammonia

405.6

113.0

Propylena

365.0

46.3

H2O

647.1

220.5

CO2

304.2

73.8

11

CHAPTER 2: 1ST LAW OF THERMODYNAMIC

Chapter 2 - Content
2.1 P-V work
2.2 Heat
2.3 1st law
2.4 Enthalpy
2.5 Heat capacity
2.6 Ideal gas & 1st law
2.7 Quantities calculation of 1st law
2.1 Work force exerted on a body so as to move it from point
x1 to x2 at distance x is defined as,

x2
w = F ( x)dx = Fx
x1
1

2.1 PV work (Continue ..)

Problem example:
A woman lifts 30.0kg object slowly to a 2.00m height from its
original position. Calculate the work done by the woman.
Solution:

x2
w = F ( x)dx = Fx
x1

= (mg )(x)

= (30.0 kg 9.81 m.s 2 )(2.00 m)

= 588 J
380,00 J/banana
2

2.1 PV work (Continue ..)

A
surrounding

system
x

PV work (reversible) pressure exerted on a body so that its

volume reduces by -V (A-x) is defined as,
2

wrev = P (T , V ) dV = PV
1

Piston contraction = surrounding does work on the system

PV work (monodirection), dwirrev = -PdV dKpist

2.1 PV work (Continue ..)

PV work of a system can be determined from graph P versus V.
P

V1

V2

2
V

V
V2

V1

P
V2
V2
V1

V1

2.1 PV work (Continue ..)

Problem example:
Calculate the reversible work (in J) illustrated by the previous
Figure if P1=3.00atm, V1=500cm3, P2=1.00atm and V2=2000cm3.
Solution:
2

wrev = P1 dV = P1V
1

= (3.00atm)(2000 500)cm3
5

1.01325 10 Nm
= 4500atm.cm
1atm
3

-2

(110 m)
-2

(1cm)

1J
1N.m

= 456J

2.2 Heat
Heat generated due to temperature difference can be computed
from the following equation,
T2

q P = m cP (T ) dT

(2.2a)

T1

where, cP is heat capacity

At constant pressure,

dqP H
CP
=

dT T P
At constant volume,

dqV U
CV
=

dT T V
6

2.3 1st Law of Thermodynamic

E=K+V+U
If kinetic energy, K and potential energy, V do not
influence the system, then total energy, E = internal
energy, U .

U = q + w
Problem example:
Calculate U (cal) for 1 mole H2O experiencing change of
temperature from 25.0 to 30.0C at 1.00atm. Water density at
25.0C and 30.0C are 0.9970 g/cm3 and 0.9956 g/cm3,
respectively. Molecular weight and heat capacity for water are
18g/mol and 1.00cal/(gC), respectively.
7

2.3 1st Law of Thermodynamic (Continue ..)

Solution:

qP = mcP T
=

18 g 1 mol H 2O 1.00 cal (30.0 25.0)C

= 90 cal.
mol
gC
2

w = P dV = P1V
1

m m
1 1
= P1 = P1m
2 1
2 1

1 cm 3
1
= (1.00 atm)(18g)

0
.
9956
0
.
9970

5
-2
110 -2 m
1J 0.23901 cal
3 1.01325 10 Nm
= 0.025 atm.cm
1atm
1J
(1cm)3 1N.m
= 0.00061 cal.

U = q + w = 90 (0.00061) cal 90 cal

8

2.4 Enthalpy, H
H is energy defined as,
H U +PV

H = U +(PV)
For constant P, closed system, and from U=q+w

H = (qP + w) + (PV) = (qP + w) + P(V)

H = (qP + w) + (-w) = qP
qP = H
For constant V, closed system, and from U=q+w

U = qV + w = qV + 0
U = qV
qV = U
9

2.5 Heat capacity, C

- difference in heat with respect to temperature change.
i. Heat capacity at constant pressure, CP

dq P H
CP
=

dT
T P
ii. Heat capacity at constant volume, CV

dqV & U #
CV
=$
!
dT
% T "V

-& U #
*& V #
CP CV = +$
! + P ($
!
,% V "T
)% T " P

..(2.2b)

..(2.5)
10

2.6 Ideal gas & 1st law

Ideal gas

1st law

PV = nRT

= 0
V T

For ideal gas,

internal energy = c
at constant T

From equation 2.5

-& U #
*& V #
CP CV = +$
! + P ($
!
,% V "T
)% T " P
and for ideal gas where internal energy difference= 0
CP,m CV,m = R

11

2.6 Ideal gas & 1st law (Continue ..)

Problem example:
0.1 mole ideal gas is operated in a cyclic process illustrated by
the following figure
P/atm
3.00

1.00

1000

2000

V/cm3

Cv,m = 1.5R and heat capacity are independent of temperature.

Calculate U for each process.
12

2.6 Ideal gas & 1st law (Continue ..)

Solution:
T1 = P1V1/(nR) = 122K, T2 = 366K, T3 = 732K, T4 = 244K.
Employing dU = CVdT
Path 1-2, dU = (0.1mol)(1.50)(8.314 J/mol.K)(366-122)K
= 304.2 J
Path 2-3, dU = (0.1mol)(1.50)(8.314 J/mol.K)(732-366)K
= 456.0 J *
Alternatively,

du = dqP + dw = ncP T + (PdV )

= (0.1)(2.5R )(732 366) (3atm)(1000cm3 )
= 456.3 J *

13

2.6 Ideal gas & 1st law (Continue ..)

Path 3-4, dU = (0.1mol)(1.50)(8.314 J/mol.K)(244-732)K
= -608.6 J
Path 4-1, dU = (0.1mol)(1.50)(8.314 J/mol.K)(122-244)K
= -152.1 J

14

2.6.1 Reversible isothermal process

For reversible isothermal & ideal gas,

U = q + w = 0, w = q
2
nRT
dV
w = q = PdV =
dV = nRT
V
V
1
1
1
2

V1
P2
= nRT ln
= nRT ln
V2
P1

..(2.6)

15

2.6.1 Reversible isothermal process (continue ..)

Problem example:
0.1 mol ideal gas (Cv,m = 1.50R) expands isothermally and
reversibly from 1.00 to 3.00L at 300K. Calculate q, w and U.

Solution:

V1
J
1

w = nRT ln
= (0.1mol) 8.314
(300K )ln = 274J
V2
mol.K
3

q = - w = 274J, U = 0

16

2.6.2 Reversible adiabatic process

U = CV (T) = w

dU = dq + dw
CV dT = ( RT / V )dV
2
CV
R
V2
V1
1 T dT = 1 V dV = R ln V1 = R ln V2
2

Assuming heat capacity is independent of temperature

CV ln

T2
V
= R ln 1
T1
V2

PV P V
Using 1 1 = 2 2
T1
T2

P1V1 = P2V2

and

CP
=
CV

17

2.7 Quantities calculation of 1st law

Summary of quantity calculation of q, w, U, H
based on a process
a. Reversible phase change at constant T and P
q = latent heat (eq. 2.2 cannot be used. During phase change
water steam, temp. remains at 100C)
w = -PV, H = q, U = q + w
b. Heating at constant pressure w/o phase change
q = eq. 2.2 = H
w = -PV, U = q + w
c. Heating at constant volume w/o change of phase
q = eq. 2.2b
w = 0, H = U +V(P), U = q
18

2.7 Quantities calculation of 1st law (continue ..)

d. State change for ideal gas (temperature change)
q = U - w

T
w = PdV = nR dV
1
1 V
2

T2

U = CV (T )dT ,
T1

T2

H = C P (T )dT
T1

e. Reversible isothermal process for ideal gas

H = U = 0
w = persamaan (2.6) , q = -w
f. Reversible adiabatic process for ideal gas
dq = 0, dw = U
H & U can be calculated using eq.(s) in d
g. Adiabatic expansion for ideal gas in vacuum
q = w = U = H = 0
19

CHAPTER 3: 2nd LAW OF THERMODYNAMIC

Chapter 3 - Contents
3.1 Heat engine
3.2 Entropy & entropy calculation
3.3 Reversible & irreversible process
Kelvin Plank/Clausius states that it is impossible to undergo
Cyclic process whose sole effects are the flow of heat into
the system from a heat reservoir and produces same amount of
work on the surroundings.
Heat
reservoir

Heat, q

Heat
engine

Work = q

To recapitulate, heat engine <100% efficiency.

1

3.1 Heat engine

- Convert heat energy into mechanical energy/work

Hot Reservoir, TH
qH
Heat
Engine

-w

-qC
Cold Reservoir, TC
Efficiency, erev
w qH qC
qC
work output from each cycle
erev

1
energy input from each cycle qH
qH
qH
erev 1, eirrev erev
2

3.1.1. Carnot cycle

1

Isothermal expansion,
T=TH

P
adiabatic

Means cyclic

2
4

adiabatic

Isothermal
compression, T=TC

Efficiency of Carnot engine

U 0 q w qH qC w
w qH qC
work output
e
heat input
qC
TC TH TC
1
1

qH
TH
TH

dq
dq dq
T 1 T 3 T 0
qH qC

0
TH TC
Proof of the integration is
given in textbook pg. 81-82

3.2 Entropy & entropy calculation

For closed, reversible process, the change in entropy,

a. Cyclic process, S = 0

dqrev
dS
T

b. Reversible adiabatic, dqrev = 0. Thus, S = 0

c. Reversible, phase change at constant T and P

dqrev 1 2
qrev H
S
dqrev

T
T 1
T
T
1
2

d. Reversible, isothermal process

S = qrev/T

3.2 Entropy & entropy calculation (continue ..)

Problem Example:
Heat evaporation for water at 100C is 40.66 kJ/mol. Calculate
S when 5.00g steam condenses to liquid at 100C and 1 atm.
Solution:
2

dqrev 1 2
qrev
S
dqrev
T
T 1
T
1
(40.66 kJ/mol)(1m ol/18g)(5. 00g)

30.27 J/K
(100 273.15)K

3.2 Entropy & entropy calculation (continue ..)

e. Reversible, change of state for ideal gas
T2

CV (T )
V2 2 CV (T )
P1T2
S
dT nR ln

dT nR ln
T
V1 T1 T
P2T1
T1
f. Irreversible state change for ideal gas S 0 since process
is irreversible. Calculation of S similar as in e.
Problem Example:
Calculate S when 24 mg N2 (g) at 89 torr and 22 C expands
adiabatically into a vacuum at 34 torr.
Solution:
T is constant, therefore,
P1T2
24mg
89
S nR ln

8.314J/mol.K ln
6.9mJ/K
P2T1 28g/mol
34
6

3.2 Entropy & entropy calculation (continue ..)

g. Ideal gas, a, is mixed with ideal gas, b, at constant T
na
where, xa
mixS na R ln xa nb R ln xb
na nb
h. Heating at constant P w/o change of phase
T2

CP
S
dT
T
T1

T2
if CP is independent of T, S CP ln
T1

Problem Example:
Calculate S when 100g water is heated irreversibly from
50C to 75C at 1 atm. CP remains constant at 1.00
cal/(gC).
Solution:
T2
T2
1.00kal
1J
348.15
S C P ln mcP ln 100g
ln
31.18J/K
T1
T1
gK 0.23901kal 323.15
7

3.3 Reversible & irreversible process

i. Reversible process heat transfer between system & surrounding
prevails w/o visible temperature change. The system &
surrounding can be returned to their initial states.
Heat into system = (dqrev)syst
Heat into surrounding = - (dqrev)surr
Thus, dSuniv=dSsyst + dSsurr = 0
Suniv = 0
ii. Irreversible process the system and surrounding cannot be
returned to their original state.
Ssyst 0, Suniv 0
Entropy increases to a maximum when the process attains
equilibrium.
(gas mixture, chemical rx., flow of heat into cold body, etc.)
8

CHAPTER 9: SOLUTION
Chapter 9 - Contents
9.1 Solution composition
9.2 Partial molar quantity
9.3 Mixing quantity
9.4 Ideal solution and thermodynamic properties
9.7 Ideally dilute solution
9.8 Thermodynamic properties of ideally dilute solution

9.1 Solution composition

Definition in solution composition calculation:
Mol fraction, xi = ni/ntot
Molar concentration, ci = ni/V
Mass concentration, i = mi/V
Solvent is usually labelled with A, whereas solute
with B or i.
Molality of solute, mB

Example:
AgNO3 (aq) containing 12.000% AgNO3 by weight has density of
1.1080 g/cm3 at 20C, 1atm. Calculate,
i.
Mol fraction
ii.
Molar concentration
iii.
AgNO3 molality

9.2 Partial molar quantity

50.0 cm3 water + 50.0 cm3 ethanol will not give
100.0 cm3 solution. In fact, the total volume
becomes 96.5 cm3 at 20C, 1atm. This is due to the
difference in partial molar volume as a result of
different force between molecules and density of the
molecules in the mixture. The differential volume, dV

The partial molar volume (single phase),

For isothermal, isobaric system

9.2 Partial molar quantity continues ..

Partial molar volume of solute can be determined
graphically by taking the slope of V against molality.
Example:
The following graph was obtained from an experiment.
Determine the partial molar volume of both solute and
solvent.

9.2 Partial molar quantity continues ..

The other partial molar quantities are,

9.2 Partial molar quantity continues ..

From G=H-TS, the following quantities can be obtained,

9.3 Mixing quantity

9.4 Determination of partial molar quantity

9.5 Ideal solution

10

9.6 Thermodynamic properties of ideal solution

11

9.6 continues ..

12

9.6 continues ..

13

9.6 continues ..

14

9.6 continues ..

15

9.6 continues ..

MW(B)= 78gmol1, MW(T)=92gmol1

16

9.7 Ideally dilute solution

17

9.7 Ideally dilute solution continues ..

18

9.7 Ideally dilute solution continues ..

19

9.7 Ideally dilute solution continues ..

20

Chapter 10: Non-Ideal Solutions

10.1 Activities and activity coefficient
In the non-ideal (real) solutions the
particles of the components interact with
each other.
There can be volume changes during mixing at
the constant pressure;
the pressure of the mixture is not equal the sum
of the partial pressures of the components; and
there are changes in internal energy (or
enthalpy) after mixing (i.e. heat is either
absorbed or released during mixing).
1

Non-Ideal Solutions

na

nb

na + nb

Emix 0, Hmix 0

Chemical Potential in Non-Ideal

Solutions
To make adjustment for the non-ideality of
the solution the chemical activity is used
instead of the concentration in the
fundamental equation for the chemical
potential.
By definition the chemical activity equals
the product of the concentration and
activity coefficient.
3

Chemical Potential in Non-Ideal

Solutions
All non-ideal solution theories are further focused
on calculating the activity coefficient.
These theories calculate the internal energy (or
enthalpy) component of the free energy of the
mixing for the non-ideal solution, take partial
derivatives and relate them to the log of the
activity coefficient.
Therefore, the activity coefficient accounts for the
changes in the internal energy (or enthalpy) during
mixing.
4

Chemical potential for ideally dilute solution

iid = io + RT lnxi
Chemical potential for non ideal solution

i = io + RT lnixi

i approaches 1 as xA approaches 1

Where i = activity coefficient,

ai is activity = ixi
From Henrys law (solute)
From Roults law (solvent)
5

From Henrys law (solute)

From Roults law (solvent)
As i approaches 1, substance A behaves as if it were ideal. If
i1, Raoult's Law is accurate.
For i>1 and i<1, substance A shows positive and negative
deviation from Raoult's law, respectively.
Positive deviation implies that the substance is more volatile.
Negative deviation implies that attraction force between A-B
pairs is stronger than between A-A and B-B pairs. As a result,
both A and B will have less tendency to escape to the vapor
phase

Example
Chloroform and ethanol vapor pressure is 295.1 and 102.8 torr,
respectively at 35C. Chloroform-ethanol solution at xethl=0.200
has vapor pressure of 304.2 torr and xethv=0.138. Find chl, eth and
achl. (chl=1.483 g/cm3, eth=0.789 g/cm3)

10.4 Activity coefficients on the molality and molar

concentration scales
Use molality (mol solute i divided by mass of solvent A, mi)
instead of mol fraction (xi) for solution containing solid or gas.
Molality of solute i, mi = ni/(nAMA)
Defining molality-scale activity coefficient, m,i = xAi

i = om,i + RT ln(m,imi/mo)
Where, mo=1mol/kg
The activities on molality
am,i = m,imi/mo
8

10.4 continues..
For molar concentration scale,

i = oc,i + RT ln(c,ici/co)

Where, co=1mol/dm3

The activity coefficient on molar concentration scale, c,i

c,i = mim,i/ci
The activities on molar concentration scale

ac,i = c,ici/co = (mo/co)am,i

9

Example
Molality-scale activity coefficient for sucrose in water is 1.292.
Its molality is 1.5 mol/kg at 25C. Calculate suc, asuc, am,suc,
ac,suc (wtr=18.01g/mol, wtr=1kg/dm3)

10

10.6 Solution of electrolytes

Let a solution containing a nonelectrolyte solvent A be H2O or
CH3OH and a solute i be Na2SO4, MgSO4 or MgCl2.

Na2SO4:

M=Na, X=SO4;

v+=2, v-=1;

z+=1, z-=-2

MgSO4:

M=Mg, X=SO4;

v+=1, v-=1;

z+=2, z-=-2

MgCl2:

M=Mg, X=Cl2;

v+=1, v-=2;

z+=2, z-=-1

Na2SO4 (1:2 electrolyte), MgSO4 (2:2 electrolyte), MgCl2 (2:1

electrolyte)

11

Let m+ and m- be the molalities of ions Mz+ and Xz-.

Chemical potential of cation

Chemical potential of anion
Where, mo=1mol/kg. For strong electrolyte,

12

Example
0.802M MgCl2 (aq) has density of 1.108g/mL. Find a for MgCl2?
(Given: MW of MgCl2=95.2g/mol, +=0.98, -=0.72)

13

10.9 Ionic association

The equilibrium for ion pair formation

Let be the fraction of ions Mz+ that do not associate with Xz-

The free Gibb energy,

14

10.11 Non-ideal gas mixture

Where fi is fugacity of a component gas i (bar)

ai = fi/Po

Po =1bar

The fugacity coefficient, , is expressed as

= fi/Pi = fi/(xiP)

15

Example
Calculate G (for ideal and non-ideal system) when 1mol N2 is
compressed isothermally from 1 to 1000atm at 0C.
(Given: at 1atm = 0.9996, at 1000atm = 1.84)

16

CHAPTER 14: ELECTROCHEMICAL SYSTEM

Contents
14.2 Electrochemical system
14.4 Galvanic cell
14.5 Types of electrodes
14.7 Standard electrode potential
14.10 Application of EMF measurements

14.2 Electrochemical system

14.2 Electrochemical system continues ..

14.2 Electrochemical system continues ..

14.4 Galvanic cell

14.4 Galvanic cell continues ..

14.4 Galvanic cell continues ..

14.4 Galvanic cell continues ..

14.4 Types of electrodes

14.4 Types of electrodes continues ..

14.7 Standard electrode potential

Standard electrode potentials is for a reference cell that
has hydrogen electrode on the left and the other electrode
types on the right in H2O measured at 25C, 1bar