Thermodynamics
CHEM2613
Chaos, Keep it Coming
Heather Ryphemi Stregay
Can you imagine how life would be
If there were no entropy?
Or, making matters even worse,
The laws of entropy were reversed?
Books would get straighter on their shelves,
And children's rooms would clean
themselves.
And every rock or stick or tree
Would form a crystal, perfectly.
There'd be no anarchy of war
For everyone would know the score.
Every thing and every face
Would have its certain time and place.
Replacing every beach would pass
An endless stretch of flawless glass.
The sea would be the brightest blue,
And every day the sky would too.
How beautiful would be our world
If order did command it.
If all were straight and never curled.
Perhaps we should demand it.
Proff J Conradie and JC Swarts
You'd think a world sans entropy
Would be a better place to be.
I said this recently myself,
As all my books fell off their shelf.
Yet pondering this ordered bliss,
I noticed things that I would miss.
Like rolling waves upon the sea,
Or sugar for my morning tea.
The sugar won't dissolve, it's true,
That anti-entropy holds like glue.
And after that, I saw with grief,
There'd be no fractaled maple leaf.
No beauty in the summer wood,
Should chaos disappear for good.
What a bore, to know each day
Would turn out in the same old way.
If entropy would disappear,
There'd be no fortune, fate or luck.
And even after many years,
Vegas wouldn't make a buck.
 CONTENTS:
1  BACKGROUND (Mortimer p 1-14, 34, 49, A26) ......................................................................3 
1.1  Introduction ...........................................................................................................................3 
1.2  The four laws of thermodynamics ........................................................................................4 
1.3  Definition System, Surrounding, Types of systems..............................................................4 
1.4  States of a system ..................................................................................................................6 
1.5  Equilibrium and reversible processes (very important) ........................................................6 
1.6  Gaslaws (Self-study) .............................................................................................................7 
1.7  Macroscopic states, Extensive and Intensive variables ........................................................7 
1.8  Maths.....................................................................................................................................7 
1.9  Homework.............................................................................................................................9 
2  WORK (w) AND CHANGE IN PRESSURE (P) (Mortimer p 43-52) ...................................10 
2.1  Definition of work, the most general expression for work, convention .............................10 
2.2  Work w done during different processes: reversible, quasi reversible and irreversible .....11 
2.3  Examples on work w done and change in pressure P (Tutorial 1) ...................................11 
2.4  Important notes on examples of work w done and change in pressure P .........................13 
2.5  Self-study and homework ...................................................................................................14 
3  HEAT (q) AND INTERNAL ENERGY (U) (Mortimer p 52-70) ............................................15 
3.1  Definitions heat, heat capacity and latent heat....................................................................15 
3.2  Internal energy (U) and the First Law of Thermodynamics ...............................................16 
3.3  q for different processes: isothermal, isochoric, isobaric and adiabatic ...........................17 
3.4  Self-study ............................................................................................................................17 
4  EXAMPLES ON DETERMINING U, q and w (Mortimer p 44-77).......................................18 
4.1  Real and ideal gasses ..........................................................................................................18 
4.2  Reversible and irreversible processes .................................................................................18 
4.3  Self-study and examples .....................................................................................................18 
5  THERMOCHEMISTRY (Mortimer p 77-90) (Calculation of enthalpy and internal energy for
chemical reactions) .............................................................................................................................22 
5.1  Definitions...........................................................................................................................22 
5.2  Calculation of H for chemical reactions, Hess's law ........................................................24 
5.3  H at various temperatures .................................................................................................25 
5.4  U for chemical reactions ...................................................................................................25 
5.5  U from average bond energies for gasses .........................................................................25 
5.6  Examples (H and U) .......................................................................................................25 
5.7  Self-study and homework ...................................................................................................26 
ADDITIONAL EXAMPLES ON CHAPTER 2.....................................................................................26 
TABLES OF SELECTED THERMODYNAMIC FUNCTIONS. .........................................................27 
6  SECOND LAW OF THEMODYNAMICS (Mortimer p 94-95, 102, 106-119) ........................28 
6.1  Spontaneous and non-spontaneous processes .....................................................................28 
6.2  Entropy (p 94-95) ................................................................................................................28 
6.3  The second law of Thermodynamics. .................................................................................29 
6.4  S for different processes. ..................................................................................................29 
6.5  Examples on calculating S................................................................................................31 
6.6  Entropy for the mixing of gasses (p 117-119) ...................................................................33 
6.7  Self-study and homework ...................................................................................................33 
7  COMBINATION OF THE FIRST AND SECOND LAW.........................................................33 
7.1  Entropy change, S, in terms of volume and temperature. .................................................33 
7.2  Entropy change, S, in terms of pressure and temperature. ...............................................33 
8  THE THIRD LAW OF THERMODYNAMICS (Mortimer p 123-127) ...................................34 
8.1  The third law of thermodynamics .......................................................................................34 
8.2  Calculation of entropy S(T1) at constant pressure P. ..........................................................34 
8.3  Standard entropy S0 .............................................................................................................35 
8.4  Examples on the third law...................................................................................................35 
1
 9  SUMMARY OF SELECTED FORMULAS FROM THERMODYNAMICS CHEM2613. .....36 
9.1  Work of expansion/compression.........................................................................................36 
9.2  Heat .....................................................................................................................................36 
9.3  Enthalpy ..............................................................................................................................36 
9.4  Entropy ................................................................................................................................36 
WORKING SCHEDULE Thermodynamics CHEM2613 ......................................................................38 

Textbook: Physical Chemistry by RG Mortimer

WORKING SCHEDULE

Lecture 1: Background (p 1-14, 34, 49)

Homework: Exercise 1.2 (b), 1.16 and the problem in 1.9 of these notes.
Lecture 2: Work and change in pressure (p 43-52)
Self-study: Example 2.1, 2.2 and 2.3
Homework: Exercise 2.1, 2.2b and 2.3a and b.
Lecture 3: Heat and internal energy (p 52-70), Note: possible classtest next lecture.
Self-study: Example 2.5, 2.6, 2.7a, 2.9, 2.12, exercise 2.12.
Lecture 4: Possible classtest (work, change in pressure, heat), p 74-77, Examples on U, q and w.
Self-study p 74-77, Example 2.13, 2.14, 2.15, 2.16
Lecture 5: Thermochemistry: Enthalpy H and internal energy U (p 77-90), Note: possible classtest
next lecture.
Homework: example 7 of paragraph 5.6 of this notes.
Self-study Example 2.17, 2.18, 2.19, 2.21, 2.23
Lecture 6: Possible classtest (chapter 2) and Examples on chapter 2.
Lecture 7: The second law (p 94-5, 102, 106-117)
Homework Exercise 3.6 (assume ideal gas) and 3.7
Lecture 8: Entropy for the mixing of gasses, examples on S (p 117-119), possible classtest next
lecture.
Lecture 9: Possible classtest (second law), Combining the 1st and 2nd law, the third law, examples
(p123-7)
Homework: Examples on the third law, paragraph 8.4 no 3) and 4).

2
1 BACKGROUND (Mortimer p 1-14, 34, 49, A26)
1.1 Introduction

Thermodynamics is the branch of science dealing with the laws and theories related to energy in the
universe. Thermodynamics is essentially concerned with the conservation of energy, and with energy
transfer, either in an organized form (work), or in a chaotic, disorganized form (heat). It predicts the
spontaneous direction of chemical processes or reactions, and the equilibrium states of chemical
systems. However, it does not deal with the rates of processes or reactions: this is the subject of
chemical kinetics. There are two main laws of thermodynamics, the first and second law. There also is
a third law as well which says that absolute zero exists, which is actually a consequence of the other
two.

Energy is defined as the ability to bring about change or to do work. Energy exists in many forms,
such as heat, light, chemical energy, and electrical energy. Thermodynamics is the study of energy.

There are two basic types of energy, kinetic energy and potential energy. Kinetic energy is energy in
motion. For example water spilling over a dam can be harnessed to do work since it is in motion. Since
the water is moving it is said to have kinetic energy. Heat and light are other examples of kinetic
energy. Potential energy is stored energy. For example the water backed up behind the dam is not
doing work, but could do work if released. Chemical energy, the energy stored in chemical bonds is
potential energy as is the electrical energy stored in a battery. All chemical reactions, indeed just about
all of the living world, are governed by two basic laws of energy or thermodynamics.

The First Law of Thermodynamics says that energy under normal conditions cannot be created or
destroyed, simply transformed or converted from one type of energy to another. Thus the total amount
of energy and matter in the universe remains constant, merely changing from one form to another.
Thus a chemical reaction such as lighting a match does not create new energy but only converts one
type of energy to another. What's happening with the match is that as the match is burnt, potential
energy is released and converted to heat and light, kinetic energy. In living cells there are many types
of energy transformations: light to chemical (photosynthesis), chemical to chemical (cellular
respiration), chemical to electrical (nervous system), chemical to mechanical (muscles). So the first
law is of fundamental importance.

The First law deals with the conservation of energy. The second law of thermodynamics is based on
experimental fact. It deals with the direction of spontaneous processes.

The Second Law of Thermodynamics is a bit more complex than the first law, but basically it says
that any time you do work, including any time you make an energy transformation, some of the
starting energy is going to be lost as heat. Put it in another way: "in all energy exchanges, if no energy
enters or leaves the system, the potential energy of the state will always be less than that of the initial
state." This is also commonly referred to as entropy. So when you drive a car some of the gasoline's
energy is lost right a way as heat, some gets turned into mechanical energy to move the car. Even some
of this mechanical energy is also lost as heat. For instance if you feel your car's tires at the end of a trip
they will be hot from friction with the road. This heat is a loss of potential energy and is a consequence
of the second law.

There are many equivalent verbal statements of the second law, such as:
 When two systems are brought into thermal contact, heat flows spontaneously from the one at
higher temperature to the one at lower temperature, not the other way round.
 Heat cannot completely converted into work for any cyclic process, but work can spontaneously be
completely converted into heat.

3
 Spontaneous changes are always accompanied by a conversion of energy into a more disordered
form.
 The entropy S of an isolated system increases during any spontaneous change or process.

The second law has major implications. First, it means that no process is 100% efficient, so there is no
such thing as a perpetual motion machine. Secondly and most important, says that living systems will
break down unless they have some input of energy. Strictly speaking the second law also says that
closed systems become more disorganized over time. Often this is expressed by the saying "entropy
tends to increase".

Entropy is a measure of disorder or uncertainty about a system.

1.2 The four laws of thermodynamics

0th law of thermodynamics: There is a uniqe scale of temperature.

1st law of thermodynamics: energy under normal conditions cannot be created or destroyed, simply
transformed or converted from one type of energy to another. (U = heat + work = q + w).

2nd law of thermodynamics: The total entrophy or disorder of a closed system increases during a
spontaneous process ( dq  TdS ).

3rd law of thermodynamics: At absolute zero the entropy S of a perfectly pure crystalline substance
is zero. (S = 0 by T = 0 K).

total energy = usable energy + unusable energy

absolute temperature
We can describe this relationship with thermodynamic terms:
H (total energy) = G (free energy) + TS (entropy)
First year, heat qP Second year, a measure of
absorbed or evolved by the Third year the randomness or
system at constant pressure disorder of a system

1.3 Definition System, Surrounding, Types of systems

1.3.1 System
This is the substance, reaction or process (i.e. the region of chemical interest) that is studied,
characterized by properties such as T, P, V, composition, etc.

4
1.3.2 Surrounding
The region outside the system is called the surrounding.

1.3.3 Boundary
The surrounding is separated from the system by a boundary. The boundary (e.g. the container if we
study a gas or a liquid) is normally considered as part of the system.

1.3.4 Closed system

A closed system is a system in which no matter can be added or removed from the system. Note there
is no limit on the flow of energy (heat or work) in or out of the system.

Real systems are of course not closed systems but instead are open systems.

1.3.5 Open system

Open systems take in or capture matter and or energy (heat or work) from the surrounding
environment.

Living things are open systems. They fight against entropy by taking in matter and energy allowing
them to stay organized. For instance a flowering plant as a seed will start out with fairly high entropy
and become more organized through time as the plant takes up energy and uses it to grow. The plant
dies and then its entropy increases again. It's not that living things violate the second law, but by doing
work they postpone its effects.

1.3.6 Isolated system

An isolated system is a system that is completely isolated from the rest of the universe, nothing,
neither energy nor matter could get in or out of the system.

1.3.7 Adiabatic system

An adiabatic system is a system thermally isolated, and so heat (q) transfer cannot occur between the
system and its surroundings. (dq = 0) Note work (w) can be performed on or by an adiabatic system.

Matter
Work Work
Heat Heat
Open System Closed System
Surroundings Surroundings

Work
Isolated Adiabatic
System System
Surroundings Surroundings
5
1.4 States of a system
The states of a system are the possible circumstances in which the system can be found. The state of a
system is specified by a number of state variables or state functions. A state variable is a property of a
system that depends only on its present state and is independent of any previous history of the system.
The state function is determined (specified) by a number of state variables.

E.g. the ideal gas

State function: _______________
State variables: _______________
Choose as dependent variable P . Then independent variables ______________
P is therefore a function of T, V and n. The equation of state of P is: P = f(T, V, n) = P(T, V, n) =
nRT
V

Note:
 Different sets of independent variables can be chosen to specify the state of a system.
nRT
 E.g. if V was chosen as dependent variable, then V = f(T, P, n) = V(T, P, n) = .
P
 The state of a system  the phase of a system!

1.5 Equilibrium and reversible processes (very important)

Equilibrium is a condition in which there is no tendency for any change to occur.

Metastable state ______________

Thermodynamic reversible process (ideal, not in real world!) is a process whose direction can be
reversed at any point by some infinitesimal change in the surroundings. (A reversible process is one
that is carried out in infinitesimal small incremental steps, such that the system remains essentially in
equilibrium at all stages during the process. Reversible processes occur so slow that it occurs
apparently over an infinite time, e.g. if it takes a person ten years to press a bicycle pump once
inwards, then the movement of the piston of the bicycle pump can be considered as reversible. A
reversible process can be considered as a sequence of equilibrium states. It is the ideal case and not
possible in real world.) A thermodynamic reversible process is a process whose direction can be
reversed at any point by some infinitesimal change in the surroundings.

Thermodynamic irreversible process ______________

(Irreversible processes always occur in a definite time, e.g. if the cylinder of a piston moves down and
the velocity of the cylinder’s movement does not equal zero m s-1, then the movement is irreversible.)

Important: Do NOT confuse CHEMICAL REVERSIBILITY with THERMODYNAMICAL

REVERSIBILITY. Chemical reversibility implies a process or reaction can occur in the forward as
well as the backward direction (usually we talk about a dynamic equilibrium at the chemical
equilibrium position). Thermodynamical reversibility mere by refers to a VERY slow rate. Of course
it is impractical for a bicycle pump to complete only one stroke every ten years. We usually
APPROACH reversible thermodynamical equilibrium processes by letting the process occur so slowly
that the laws of equilibrium thermodynamics still hold approximately. The reader must understand
clearly that a TRUE thermodynamic equilibrium process exists only in one’s imagination. In practice
it is unattainable.

6
1.6 Gaslaws (Self-study)
Absolute temperature scale: TK  TC  273.15 K

Dalton: P  P1  P2  P3  .....

Ideal gas law PV  nRT

 n2a 
Van der Waals equation of state:  P  2 V  nb   nRT
 V 
1.7 Macroscopic states, Extensive and Intensive variables

Thermodynamics is a science of the macroscopic world. That is, it requires no prior understanding of
atomic and molecular structure, and all its measurements are made on materials macroscopically. An
understanding and study of microscopic molecular phenomena called statistical thermodynamics,
however, leads independently to the same concepts of thermodynamics. Statistical thermodynamics
is a course in chemistry IV.

E.g. consider the steam in a kettle of boiling water. A description in molecular (microscopic) terms
would involve the position and nature of each particle, and its velocity at any instant. As there would
be well over 1021 molecules present, this would be a humanly impossible task. On the macroscopic
scale, however, we are glad to find that the chemical composition of steam, its temperature and
pressure, for example, are quite sufficient to specify the situation.

Macroscopic state variables: _____________________________

Microscopic state variables: _____________________________
Extensive macroscopic state variable: _____________________
Intensive macroscopic state variable: ______________________
Gibbs phase rule: _____________________

Example: ideal gas PV = nRT

Therefore the equilibrium macroscopic state of a one-component (c=1), one-phase system is specified
by the values of three macroscopic, independent variables of which at least one must be extensive.

1.8 Maths
1.8.1 Calculus
Differentiation. Integration.
d(xn) = n xn-1 dx d(u/v) = (v du - u dv)/v2 x n 1 dx
 x dx 
n

(n  1)
 x
 ln x

d(sin x) = cos x dx d(cosec x) = - cot x cosec x dx

 e dx 
ax e ax  ln xdx  x ln x  x
a
d(cos x) = - sin x dx d(sec x) = tan x sec x dx
 sin xdx   cos x  cos xdx  sin x
d(tan x) = sec2x dx, d(cot x) = - cosec2 x dx
 tan xdx   ln cos x  cot xdx  ln sin x
d(eax) = a eax dx, d(ln x) = dx/x * *remember: lnx = 2.303 logx

7
1.8.2 Calculus with several variables: (Appendix B on p A26)
 f   f   f 
If f=f(x, y, z) then df    dx    dy    dz
 x  y , z  y  x , y  z  x , y
 f 
Note, the term   is called the partial derivative of f with respect to one of the independent
 x  y , z
variables x and is obtained by ordinary differentiation of f to x, treating all other independent variables
(y, z) as though they were constants.

Another way of looking at it as follow:

df  f keeping
due to the change in x ,
y and z cons tan t
 f due to the change in y ,
keeping x and z cons tan t
 f due to the change in z ,
keeping x and y cons tan t

 f  y ,z  f  x , y  f  x , y

 f   f   f 
   dx    dy    dz
 x  y ,z  y  x , y  z  x , y

E.g. For a simple one-phase, one-component system at equilibrium U = U(T, V, n) [or U = U(T, P, n)]
 U   U   U 
dU    dV    dn    dT
 V  n ,T  n V ,T  T  n ,V
In a nonrigorous fashion, we "divide" the above equation by dT and specify that P and n are fixed.
This gives the correct relationship between the derivatives:
 U   U   V   U   n   U   T 
             
 T  P , n  V  n ,T  T  P , n  n V ,T  T  P , n  T  n ,V  T  P , n

 T 
The derivative of T with respect to T is equal to unity [    1 ], and the derivative of n with
 T  P , n
 n 
respect to anything is equal to zero [    0 ] if n is fixed.
 T  P , n
 U   U   V   U 
       
 T  P , n  V  n ,T  T  P , n  T  n ,V

1.8.3 Exact and inexact differentials

Exact differential is path independent, it depend only on the starting and final point. Examples of exact
differential used in CHEM 214 (Thermodynamics) : dP, dV, dU, dH, dS
 dP  P  Pfinal  Pstarting (and not P)
c

Inexact differential is path dependent, it depend on the path of integration, as well as the starting and
final point e.g. dw and dq.
 dw  w (and not w!!!)
c

8
1.8.4 Averaging procedures
N m m
1 1 Ni
w 
N
w
i 1
i 
N
N w   p w
i 1
i i
i 1
i i with pi 
N

1.9 Homework
(a) Exercise 1.2 (b) (2.87%), 1.16 (78%)

 P   dP 
(b) Given P = P(V,T,n), write an expression for dP,   and  
 T V ,n  dV  T

9
2 WORK (w) AND CHANGE IN PRESSURE (P) (Mortimer p 43-52)

2.1 Definition of work, the most general expression for work, convention

2.1.1 Definition of work:

The amount of work done on an object equals the force exerted on the object times the distance the
object is moved in the direction of the force:
dw = Fzdz

OR if the force and the displaCHEMent are not in the same direction
dw = F . dr = Fdr cos  = Fxdx + Fydy + Fzdz

and w   dw   Fx dx  Fy dy  Fz dz 
c

Note:
 F . dr is the scalar product of the vectors F and r.
  is a line integral = integral carried out along the curve or path determined by the motion of the
c

object.

2.1.2 Convention
If a system is doing the work (w) on the surroundings, w is negative for the system since it loses work
energy. If work is done on a system by the surroundings, the work is considered positive for the system
since it gained energy. In calculating w, we normally refer to the system.
Surroundings

- work
Note: dwsys = - dwsurr
System Notation: dw = dwsys
+ work

2.1.3 Types of work

There are many different types of work, and all of these can change the internal energy of the system.
For example: mechanical work = force x distance
electrical work = voltage x charge
work of compression = pressure x volume change

2.1.4 Derivation of he most general expression for work of expansion/compression

dw = -Pext dV
Consider a closed one phase, one component system confined in a cylinder fitted with a piston (area
A). Let an external force Fext be exerted downwards in the z-direction on the piston (including any
force on the piston due to gravity or atmospheric pressure). Let Pext, the external pressure on the
system, be defined to be positive.

10
 -Fext
Derivation:
work done on the system
dwsys = + Fext dz
=________________
=________________
= - Pext dV
System -dz

Note:
 A system for which the equation dwsys = - Pext dV holds, is called a simple system.
 The work done is determined by the external pressure Pext, and not by the pressure of the system Pint.

2.2 Work w done during different processes: reversible, quasi reversible and irreversible
Irreversible processes:
dwirr   Pext dV NOTE: NO GAS LAWS MAY BE USED TO CALCULATE Pext!!!
Example: Determine the amount of work done for an irreversible process at constant external pressure
Pext. ( ANSW: wirr = - Pext (V2 - V1) ).

Quasi reversible processes: _____________________________

Reversible processes: _____________________________

Note: Infinitely slow, ideal situation, sequence of equilibrium processes, not in real world.
Pext = Pint, dwrev   Pint dV , GAS LAWS may be used to calculate Pint

2.3 Examples on work w done and change in pressure P (Tutorial 1)

1. A sample of O2 gas is compressed from a volume of 30 L to 5 L at constant external pressure

of 1 atm (101 325 Pa). Calculate the work done on the system. (2 533 J)

ANSW:
dw   Pext dV
V2
1 L = 1 dm3 = 10-3 m3
w   dw   ( Pext dV )   Pext (V2  V1 )
c V1

2. Determine the amount of work done on a closed system of 1 mol of an ideal gas that is
compressed reversible and isothermal at 25°C from a volume of 20 L to a volume of 5 L.
(3436 J)

11
ANSW: (reversible: gas laws may be used, isothermal: constant temperature)
dw   PdV
V2 V2 V2
nRT dV V2
w   dw   (  PdV )   (  )dV   nRT  ( )   nRT lnV   nRT ln
V2
V1
c V1 V1 V V1 V V1

3. One mole ideal gas is reversible cooled down at constant V from 298 K to 149 K; then it is
compressed isothermal from 20 L to 5 L; then it is heated reversible at constant V from 149
K to 298 K. Determine the work done on the system. (1717 J)
dx
ANSW:
nRT
 x
 ln x
dwtotal  dw1  dw2  dw3   P1dV1  P2 dV2  P3dV3  0  dV  0
V x n 1
 x dx 
n
V2

w   dw   (
nRT V
dV )   nRT lnV V2   nRT ln 2
V (n  1)
c V1 V 1
V1
d(xn) = n xn-1 dx

4. Calculate the change in pressure, P, for 2. (372 kPa)

ANSW: Ideal gas: PV = nRT, therefore take P = P(V,n,T) since R is a constant, and according to the
Gibbs Phase rule a one-component, one-phase system is specified by the values of c+2 = 3
macroscopic, independent variables.
 P   P   P 
dP    dV    dn    dT
 V  n ,T  n V ,T  T  n ,V
 P 

V2
 dV
 V  n ,T P   dP   nRT  V  2 dV
V1
  nRT 
   dV  1 
2 V
V  V  n ,T   nRT ( )
 V  V1
 1
 nRT   dV  1
V  V  n ,T 1
 nRT   

 nRT  V  2 dV   V2 V1 
  nRTV  2 dV

An easier way to answer this question:

Since P is path independent,
final and initial pressure can be used.
Ideal gas, use ideal gas law.
P  P2  P1
nRT nRT
 
V2 V1
1 1
 nRT   
 V2 V1 

12
5. Calculate the change in pressure, P, for 3. (372 kPa)

ANSW:
Ptotal  P1  P2  P3
 P   P   P  
Pi   dPi where dPi    dV    dn    dT 
 V  n ,T  n V ,T  T  n ,V  i

Easier : Since P is path independent, final and initial pressure can be used. Ideal gas, use ideal gas law.

 1mol 8.314 Jmol 1K 1 298.15K 

nRT nRT  1 1 
P  P2  P1    3
 371822 Pa  371.822kPa
 
3
V2 V1 0. 005m 0. 020 m

6. Calculate the amount of work done on the system if the isothermal process of 2 is carried out
at a constant external pressure of 1 atm instead of reversibly (i.e. irreversible), but with the
same initial and final states as 2. (1520 J)
V2

ANSW: dwirr   Pext dV therefore wirr   dwirr   ( Pext dV )   Pext (V2  V1 )

c V1

2.4 Important notes on examples of work w done and change in pressure P

2.4.1 Inexact differentials or path functions

Note that from examples 2 and 3 above that the system is in both cases in the same initial and final
states, but the final state was obtained by two different paths. It is clear that the work done depends on
the path. Work can therefore not be a state function (see paragraph 1.4), but is called a path function
instead. We will see later that the same apply to heat.
Examples Inexact differentials dw and dq.
Path functions w and q.
Therefore  dw  w
c
;  dq  q (and not w or q!!!) ;
c

2.4.2 Note on exact differentials and state functions

The system in examples 4 and 5 above is in both cases in the same initial and final states, but the final
state was obtained by two different paths. It is clear that the change in pressure on the system does not
depend on the path. Pressure is therefore a state function (see paragraph 1.4), and dP is an exact
differentials (see paragraph 1.8.3).
Examples Exact differentials dP, dV and dU.
State functions P, V and U.
Therefore  dP  P  Pfinal  Pstarting ;  dV  V  V final  Vstarting ;  dU  U  U final  U starting
c c c

Note: (P, V, and U, and not P, V or U)

2.4.3 Note on work done during irreversible and reversible processes.

Note that from examples 2 and 6 above that wirr < wrev. This result is an example of a general
principle which can be stated as: A system operating between specified initial and final states does the
maximum work when the process is carried out reversibly. (As the expansion of the gas proceeds, at a
constant temperature, so its pressure drops. At any stage of the process, the amount of work it can do
is determined by the opposing external pressure. If the opposing pressure is allowed to drop too
quickly (as in an irreversible expansion of a gas), less than the theoretical maximum work is done.)

13
2.4.4 Summary work
Irreversible processes: dwirr   Pext dV NO GAS LAWS may be used to calculate Pext
Reversible processes: dwrev   Pint dV GAS LAWS may be used to calculate Pint

2.5 Self-study and homework

Self-study: Example 2.1, 2.2 and 2.3
Homework: Exercise 2.1, 2.2b and 2.3a and b

14
3 HEAT (q) AND INTERNAL ENERGY (U) (Mortimer p 52-70)
3.1 Definitions heat, heat capacity and latent heat
HEAT (q) is defined as the energy that flows in or out of a system due to a difference in
temperature between the system and its surroundings.

Note:
 TEMPERATURE is defined as the degree of hotness.
 q is positive if heat is absorbed by the system
 q is negative if heat is evolved from the system
 When the sign of q is determined, we refer to the system and not to the surroundings.
Surroundings

heat flows
out of system
-q
System
heat flows
into system
+q

Summary of conventions apply to the signs of q and w:

q=+ Heat is absorbed by the system
q= Heat is evolved (given off) by the system
w=+ Work is done on the system by the surroundings
w= Work is done by the system on the surroundings

LATENT HEAT is the heat absorbed or given out by a system during a phase transition at constant T,
measured in cal g-1 or kilojoules per kilogram . (Do exercise 2.6 page 53).

HEAT CAPACITY (C) is the amount of heat q required to raise the temperature of the substance or
system by 1 C or 1 K.
q dq
C= or C = measured in J K-1 or J C-1
T dT

SPECIFIC HEAT CAPACITY (c) is the amount of heat required to raise the temperature of
1 g of a substance with 1 C or 1 K.
C heat capacity
c= = measured in J K-1 g-1 or J C-1 g-1
m mass of subs tan ce

MOLAR HEAT CAPACITY ( C ) is the amount of heat required to raise the temperature of
1 mole of a substance with 1 C or 1 K.
C heat capacity
C = = measured in J K-1 mol-1 or J C-1 mol-1
n moles of subs tan ce

REMEMBER
 T (measured in K) = T (measured in °C)

15
 c of water = 4.184 J K-1 g-1 (which means that you need 4.184 J to raise the temperature of 1 g of
water with 1 K)
 4.184 J = 1 calorie
 C varies for different substances, for different phases (e.g. solid, liquid, gas) and in general will
vary with temperature and pressure (although is does not for an ideal gas)
 c and C is constant for a specific substance in a specific phase and T, not C
 C is an intensive property, C an extensive property (paragraph 1.7).

NOTE: Water has a large c. Most c’s are smaller than 1. Example: When a car is parked in the sun
next to a fishpond, the plastic seat of the car is much warmer than the water in the pond even though
the same sun heated both. This indicated that plastic has a much smaller c than water – less energy is
required to heat the plastic with 1 degree than the water.

Therefore, if an object is heated without any chemical reaction or phase change occurring, the quantity
of heat transferred to the object is given by
T2

q   dq   CdT (See example 2.5 page 53).

c T1
T2 T2 T2

From the above definitions of c and C it follows that q   dq   CdT   mcdT   nCdT
c T1 T1 T1

3.2 Internal energy (U) and the First Law of Thermodynamics

The First Law of Thermodynamics says that energy under normal conditions cannot be created or
destroyed, simply transformed or converted from one type of energy to another, either in an organized
form (work), or in a chaotic, disorganized form (heat).

The total internal energy (U) of a closed system is the energy it contains as result of its physical state,
that is, under specified conditions of T, P and V etc. The First Law of Thermodynamics says that the
energy of a closed system is constant, unless it is changed by work, w, or by heat transfer, q:

U = q + w or dU = dq + dw

Note:
 U = q + w applies only to a closed system whose center of mass is not accelerated, gravitational
potential energy is constant and rest mass is constant.
 U = q + w is the mathematical expression of the First Law of Thermodynamics.
 For a simple equilibrium one-phase system containing one component, we can write the internal
energy U = U(T, V, n) or U = U(T, P, n) because it has c+2 = 3 independent variables.
 U is a state function. dU an exact differential.  dU  U  U final  U starting
c

q2, w2
U is a function of
State 1 q1, w1 State 2 state only (independent
U1 U2 of route taken):
U = q1 + w1
= q2 + w2
q3, w3 = q3 + w3
= Ufinal – Ubegin

16
3.3 q for different processes: isothermal, isochoric, isobaric and adiabatic
Isothermal process (constant temperature), ideal gas UT = 0 per definition.
V
Isothermal process, ideal gas, reversible: Derivation q T  nRT ln 2 ______________________
V1
Constant volume (isochoric) process: Derivation dqV  CV dT  dU ______________________

Constant pressure (isobaric) process: Derivation dqP  CP dT  dH ______________________

Ideal gas, closed system: Derivation CP  CV  nR ______________________

 1
T2  V1  CP
Adiabatic process, reversible, ideal gas: Derivation   with   ____________
T1  V2  CV
Some important notes:
 Temperature dependence of Cp: For some systems (e.g. monoatomic gasses such as Ar), Cp is
independent of temperature. However, for most systems the heat capacity varies in quite a complex
way with temperature. Within the gas phase, we can use an empirical form for the temperature
c
dependence of Cp: C p  a  bT  2 . Values of the constants a, b, and c are listed for many
T
elements in textbooks.
 Enthapy H a state function: Since enthapy H = U + PV is defined in terms of U, P and V which
are all state functions, H is also a state function. Therefore: H   dH   C p dT is path
c c

independent.
 q is a path function:  dq  q
c
(and not q!!!)
 1
 1
T2  V1  T1  P1  
   can also be rewritten as  
T1  V2  T2  P2 
V2
 Summary q: q T  nRT ln Isothermal process, ideal gas, reversible
V1
dqV  CV dT  dU
dqP  CP dT  dH
CP  CV  nR Ideal gas, closed system

3.4 Self-study
c
Examples 2.5, 2.6, 2.7a, 2.9, 2.12, exercise 2.12 (a) Given C p  a  bT  , determine q.
T2

17
4 EXAMPLES ON DETERMINING U, q and w (Mortimer p 44-77)
4.1 Real and ideal gasses
n 2a nRT n 2a
Van der Waals equation for real gasses: (P + )(V – nb) = nRT gives P = - .
V2 V  nb V 2

 U   P 
Accept the identity    T   P . Calculate U, w and q for an isothermal, reversible
 V T  T  n ,V
compression of 1 mol of CO2 at 300 K from 20 L to 5 L if
a) CO2 is an ideal gas (0, 3457.7 J, -3457.7 J)
b) CO2 is a Van der Waals gas. Given a = 0.3640 Pa m6 mol-1 and b = 0.00004267 m3 mol -1 for
CO2. (-54.6 J, 3419J, -3474 J)
c) CO2 is a Van der Waals gas but compression is irreversible (instead of reversible) and carried
out at a constant external pressure of 1 atm (-54.6 J, 1520 J, -1574.6 J)

4.2 Reversible and irreversible processes

One mole of an ideal gas, initially at 298 K and 2 atm, expands adiabatically to a final pressure of 1
atm. a) reversible and b) against a constant pressure of 1 atm (this means an irreversible process)
Take CP = 20 J K-1 mol-1 and assume CP is temperature independent.
Calculate for both processes (i) the final temperature, (ii) U, (iii) w, (iv) q and (v) H.
ANSW (a) 223.4 K, -871.78 J, -871.78 J, 0, -1492 J; (b) 236.0K, -724.53 J, -724.53 J, 0, -1240

4.3 Self-study and examples

p 74-77, Example 2.13, 2.14, 2.15, 2.16

18
Example on the calculation of q, w, U, P of an IDEAL GAS for different processes.
n mole of an ideal gas change from a state 1 defined by (V1, P1, T1) to a state 2 defined by (V2, P2, T2).. (Note n1 = n2 = n = constant and ideal gas).
a. if it is a reversible expansion b if it is a irreversible expansion c if it is a irreversible expansion against a constant external pressure
Note: Ideal gas: PV = nRT. According to the Gibbs Phase rule a one-component, one-phase system is specified by the values of c+2 = 3 macroscopic,
independent variables. Therefore use P = P(V ,n, T) or U = U(P,n,T) or U = U(P,n,V) or U = U(V,n,T), depending on the type of process considered.

process (a) reversible expansion (b) irreversible expansion (c) irreversible expansion against
constant Pext
Pext = Pint Pext Pint, Pext = constant
nRT use Pext in calculation of use Pext in calculation of
use Pint  in calculation of
V w =  dw   (  Pext dV ) w =  dw   ( Pext dV )   Pext  dV
w =  dw   (  Pext dV ) and in calculation of P nRT nRT
use Pint  in calculation of P use Pint  in calculation of P
V V
isothermal (U)T = 0 = q + w (U)T = 0 = q + w (U)T = 0 = q + w
(constant T) wsystem,reversible = w =  dw   (  Pext dV ) wsystem,irreversible = w = wsystem,irreversible = w =  dw   (  Pext dV )
V2
 nRT V  dw   (  Pext dV ) w =  Pext  dV   Pext ( V2  V1 )
=  (  Pint dV )  V V dV  nRT ln V12 Pext(V, n, T) must be known to
1 determine integral.
V2 qsystem,irreversible = q = -w =  ( Pext dV ) qsystem,irreversible = q = -w = Pext ( V2  V1 )
qsystem,reversible = q = -w = nRT ln
V1
P = P(V ,n, T) same as (a) same as (a)
 P   P   P   P 
dP    dV    dn    dT    dV
 V  n ,T  n V ,T  T  n ,V  V  n ,T
 P    nRT 
V2

P   dP     dV   V   dV
 V  n ,T V1
V  n ,T

V2 V2

 nRT 
V
1
  dV 
 nRT   V  2 dV 
V1  V  n ,T V1

 1 1
V
 1 
2

 nRT ( )  nRT   
 V  V1  V2 V1 
19
process (a) reversible expansion (b) irreversible expansion (c) irreversible expansion Pext = const
isochloric wsystem,reversible = w =  dw   (  Pext dV ) wsystem,irreversible = w = wsystem,irreversible = w =  dw   (  Pext dV ) = 0
(constant V)
=  (  Pint dV )  0  dw   (  Pext dV ) = 0
P = P(V ,n, T) same as (a) same as (a)
 P   P   P 
dP    dV    dn    dT
 V  n ,T  n  V ,T  T  n ,V
 P 
  dT
 T  n ,V
 P    nRT 
V2

P   dP     dT   T   dT
 T  n ,V V1
V  n ,V
nR 
T2 T
nR 2
T n,V dT
V T1 T V T1
  dT

 T T1
nR T2

nR
T2  T1 
V V
qV   dqV   CV dT =(U)V same as (a) same as (a)

U   dU   dq  dw V V
same as (a) same as (a)

  dq  PdV    dq  0 

V V

  dq   C dT
V V

isobaric q   dq   C dT   dH
P P P
same as (a) same as (a)
(constant
Pint) wsystem,reversible = w =  dw   ( P ext dV )   ( Pint dV ) wsystem,irreversible =  dw   (  Pext dV ) wsystem,irreversible = w =  dw   (  Pext dV )
=  P  dV   P (V  V )
int int 2 1
Pext(V, n, T) must be known to deter- w =  Pext  dV   Pext ( V2  V1 )
Note: Pext mine integral; Pint is constant, not Pext
not
P  Pint   dPint  0 same as (a) same as (a)
necessarily
constant U = q + w OR same as (a) same as (a)
U   dU   CV dT   C P  nR dT
20
process (a) reversible expansion (b) irreversible expansion (c) irreversible expansion Pext = const
adiabatic q   dq  0 q   dq  0 q   dq  0
(dq = 0)
wsystem,reversible = w =  dw   (  Pext dV ) wsystem,irreversible = w = wsystem,irreversible = w =  dw   (  Pext dV )
V 2 ,T2
 nRT ( V )  dw   (  Pext dV ) w =  Pext  dV   Pext ( V2  V1 )
=  (  Pint dV )   dV Pext(V, n, T) must be known to
V
V1 ,T1 determine integral.
T(V) must be known to determine integral.
P = P(V,n,T) same as (a) same as (a)
 P   P   P 
dP    dV    dn    dT
 V  n ,T  n  V ,T  T  n ,V
 P   P 
  dV    dT
 V  n ,T  T  n ,V
  P   P  
P   dP      dV    dT 
  V  n ,T  T  n ,V 
  nRT    nRT 
V2 T2

   dV   T   dT
V1
V  V  n ,T T1
V  n ,V
 nR 2 
V2 T
1
 nRT  T n,V dT
V T1 T
  dV 
V1
V  V  n ,T

 nRT   V dV  nR
V2 T2

V T1
2
dT
V1
V
 1 
T T1
2
nR T2
 nRT ( ) 
 V  V1 V
 1 1  nR
 nRT     T2  T1 
 V2 V1  V
U = q + w = w OR U   dU   CV dT same as (a) same as (a)

OR from U = w :   Pint dV   CV dT
21
5 THERMOCHEMISTRY (Mortimer p 77-90)
(Calculation of enthalpy and internal energy for chemical reactions)

5.1 Definitions
Consider a chemical reaction. Since most chemical reactions takes place at constant (atmospheric)
pressure, the heat qP absorbed or evolved by the system when the reaction takes place is the reaction
enthalpy change rH, sometimes abbreviated as reaction enthalpy (subscript r) or H.

5.1.1 Exo- and endothermic reactions

An exothermic reaction is where heat is evolved (q = ) by the system. An endothermic reaction is
where heat is absorbed (q = +) by the system.
When the reaction takes place at constant P, we speak of enthalpy change, rather than of heat evolved
or absorbed:
H negative  heat released  exothermic reaction
H positive  heat absorbed  endothermic reaction

Adiabatic reaction - effect on system

H negative (exothermic reaction)  heat released from system  T of system rises
H positive (endothermic reaction)  heat absorbed by system  T of system falls

Isothermal reaction - effect on surrounding

H negative (exothermic reaction) heat released from system  T of system stay constant  T of
surroundings rise
H positive (endothermic reaction)  heat absorbed by system  T of system stay constant  T of
surroundings falls

5.1.2 Standard state of a substance, standard state reaction

The standard state of a substance is specified to be the pure substance at a fixed pressure of P0 =1
bar = 105 Pa. Real gasses are to be taken ideally in their standard states, therefore the standard state of
a gas is defined as the ideal gas at P0 =1 bar.

An standard state reaction is one in which all substances are in their standard states before and after
the reaction took place. The enthalpy change for a standard state reaction is denoted by Hr0 or H0.

5.1.3 Standard state enthalpy of formation

H0f(substance) is the standard state enthalpy change of formation of a substance at a specified
temperature, sometimes abbreviated as standard state enthalpy of formation. H0f(substance) is
defined to be the enthalpy change of the chemical reaction in which the specific substance is formed
from the appropriate elements in their most stable form states at a specific T. H0f values at 298K
have been determined for many compounds and are tabulated in many textbooks (see table p26). Note
o
that the tabulated values are the molar value  H f in the units kJ mol-1. H0f values are defined to be
zero for all elements in their standard states at any temperature.

molar standard
o
change H f
formation
enthalpy

22
Example: The standard state enthalpy of formation of C2H5OH(l) is –277.67 kJ/mol and the standard
state chemical reaction for the formation of C2H5OH(l) is:
o
2C(s) + 3H2(g) + ½ O2(g)  C2H5OH(l) H f = –277.67 kJ mol-1
o
(Note, the unit of  H f is in kJ mol-1 since 1 mol of C2H5OH(l) is formed in the formation reaction).

5.1.4 Heat of combustion

Heat of combustion in kJ mol-1 is the heat released where 1 mole of the substance is burnt (in other
words reacts with oxygen). The products of combustion is usually CO2(g). If the compound contains
hydrogen , H2O(l) is also a product.

Example: The thermochemical equation for the combustion of glucose and for graphite is:
C6H12O6(s) + 6O2(g)  6CO2(g) + 6H2O(l) H o = –2803 kJ
C(graphite) + O2(g)  CO2(g) H o = –393.5 kJ
o
The molar heat of combustion,  H , of glucose and graphite is -2803 kJ mol-1 and –393.5 kJ mol-1
respectively.

5.1.5 The enthalpy of phase changes.

The heat released during a phase transition is sometimes called latent heat, because it does not change
the temperature of the system. The amount of latent heat per unit mass is characteristic of the substance
and the phase transition. In the case of constant-pressure phase transitions, this heat is the enthalpy of
o
phase transition/ change,  H latent in J/g. The specific enthalpy changes for reversible fusion
(melting) and vaporization (boiling) are positive, and the enthalpy changes for reversible freezing or
condensation are the negatives of these values.
Examples: H2O(l)  H2O(g) H o vap = +2257.5 J/g = +40.67 kJ mol-1
H2O(g)  H2O(l) H o condensation = –2257.5 J/g = – 40.67 kJ mol-1
H2O(s)  H2O(l) H o fus = +333.5 J/g = + 6.01 kJ mol-1
H2O(l)  H2O(s) H o freezing = –333.5 J/g = –6.01 kJ mol-1
The latter means 333.5 J/g of heat is released when 1 mol of liquid water freezes at constant P and T.

5.1.6 The enthalpy changes of nonchemical reactions.

T2

For a constant-pressure process in a closed system H  q P   dq P   C P dT

T1

(constant n and P, no phase transition, no chemical reaction, e.g. the heating of a system)

Example: Calculate the amount of heat required to heat 3 mol of liquid water at 90°C to 100°C.
(Given: Cp(water) = 75.48 J K-1 mol-1)

H  H l ( 90C  100C )
Tg Tg
 J 
  nC p ( liquid )dT   3mol  75.48 dT
T1 T1  molK 
Tg
 J   J 
T2  T1 
molK  T1
 3mol  75.48  dT  3mol  75.48
  molK 
 J 
 3mol  75.48 373  363  4528.8 J
 molK 

23
5.1.7 The enthalpy changes when heating a substance at constant pressure.
The enthalpy change, H, for heating a substance from T1 to T2 at constant P if no phase transitions
occur:
T2 T2 T2 T2

H   dH   dq p   C p dT   nC p dT with Cp = heat capacity of the substance at constant pressure.

T1 T1 T1 T1

General, if phase transitions occur, H for heating a substance from T1 to T2 at constant P can be
calculated by:

H  H s ( T1  Tm )  H melt  H l ( Tm  T g )  H vap  H g ( T g  T2 )
Tm Tg T2

  nC p ( solid )dT  n H melt   nC p ( liquid )dT  nH vap   nC p ( gas )dT

T1 Tm Tg

where: Tm = reversible melting temperature, Tg = reversible evaporation temperature

Hfuss/melt = enthalpy change for fusion (melting), Hvap = enthalpy change for evaporation
Cp(solid) = heat capacity for solid phase, s = solid, l = liquid, g = gas

Example: The heat, qp = H, necessary for heating water from ice at T1 = -10°C (263K) to water
vapor at T2 = 120°C (393K):
H  H s ( 10C  0C )  H smelt  H l (0C  100C )  H verdamp  H g (100C  120C )
Ts Tg T2 120 C

  nC
T1  1 C
p ( solid )dT  n H smelt   nC p (liquid ) dT  nH verdamp 
Ts
 nC
Tg
p ( gas )dT

T Tg T
 J   J 
 
s 2

  n 33 dT  nH smelt   n 75.48 dT  nH verdamp   n a  bT  cT dT

2

T1   Ts  
molK molK Tg

T2
 
T g  Tm   nH verdamp  n aT 
 J   J  bT 2
 n 33 Tm  T1   nH smelt  n 75.48  cT 1 
 molK   molK   2  Tm

T g  Tm   n 40670
 J   J   J   J 
 n 33 Tm  T1   n 6010   n 75.48 
 molK   mol   molK   mol 
 J 0.0103 J 
 n 30.5 (T2  Tm )  (T 2 2  Tm )  0 
2

 
2
Kmol 2 K mol
 J   J   J   J 
 1mol  33 273K  263K   1mol  6010   1mol  75.48 373K  273K   1mol  40670 
 molK   mol   molK   mol 
 J 0.0103 J 
 1mol  30.5 (393K  373K )  (393 2 K 2  373 2 K 2 ) 
 
2
Kmol 2 K mol
 330  6010  7548  40670  610  79  J
 55247 J  55 kJ
(REMEMBER: Water freezes at 0°C (273 K) and boils at 100°C (373 K) at 1 atmosphere pressure).

5.2 Calculation of H for chemical reactions, Hess's law

The standard state enthalpy change of an overall reaction is the sum of the standard enthalpies changes
of the individual reactions into which the reaction may be divided.
H o   i H o f (i )   H o f ( products)   H o f (reac tan ts )
i prod react

i > 0 for products, i < 0 for reactants.

24
5.3 H at various temperatures
An enthalpy change at a temperature other than found in tables, can be calculated by Kirchhoff's rule:
T2 T2

H (T2 )  H (T1 )   dH  H (T1 )   C P dT

T1 T1

with CP   iCP (i )   CP ( products)  CP (reac tan ts )

i

Note, that if the CP are temperature independent, then H (T2 )  H (T2 )  C P (T2  T1 )

5.4 U for chemical reactions

From the definition of H = U + PV, it follows that U  H  (PV ) .
For liquids and solids: ( PV )  0 and U  H
For gasses:
( PV )  n( g ) RT if the products and reactants are at the same T
with n(g) = (sum of amount of gas moles in product) - (sum of amount of gas moles in reactants)
therefore: U  H  n( g ) RT for gasses

5.5 U from average bond energies for gasses

U  (sum of all bond energies in reactants) - (sum of all bond energies in product)

Note:
 Bond energies are tabulated in many text books (see table p26)
 The value obtained of U from average bond energies is ordinarily used for H without correction
for the value of (PV) from, see e.g. example 2.23 on p89.
 If the question states: estimate U for a chemical reaction, then use average bond energies.
 If the question states: calculate U for a chemical reaction, then use U  H  n( g ) RT .

5.6 Examples (H and U)

1 Calculate the value of the standard-state enthalpy change, H0, of the following reaction
CaCO3(s)  CaO(s) + CO2(g) (178 kJ/mol)
2 The standard-state enthalpy change of combustion of C2H6 (ethane) is 1561 kJ/mol at 298K.
0
Calculate the enthalpy change of formation,  H f (C 2 H 6 (g)) , of ethane at 298K. (-85 kJ/mol)
3 Determine the standard-state enthalpy change of the formation reaction of methane (CH4). (-
74.9 kJ/mol)
4 Calculate the value of the standard-state enthalpy change of the following reaction at 200°C
(473K): CaCO3(s)  CaO(s) + CO2(g) (177 475 J/mol). Assume that Cp is temperature
independent.
5 Calculate U0 for the following reaction at 298 K:
C2H2(g) + 5/2 O2(g)  2CO2(g) + H2O(l) (-1297 kJ)
6 Given the following reaction: CH4(g) + 2O2(g)  CO2(g) + 2H2O(g)
6.1 Using the average bond energy values, estimate U for the above reaction. (-794 kJ)
6.2 Calculate H298K for the above reaction (-803 kJ)
6.3 Calculate U298K for the above reaction (-803 kJ)
7 Given the reaction: H2(g) + ½ O2(g)  H2O(g). Estimate U, calculate H and U at 298K.

25
5.7 Self-study and homework
Homework: example 7 of paragraph 5.6 of these notes, Exercise 2.30 page 90 in Mortimer.
Self-study: Example 2.17, 2.18, 2.19, 2.21, 2.23

ADDITIONAL EXAMPLES ON CHAPTER 2

1 Calculate H0 for the reaction FeO(s) + 2H+(aq)  H2O(l) + Fe2+(aq)
if 2Fe(s) + 1½ O2(g)  Fe2O3(s) H0 = -822 kJ eq 1
2FeO + ½ O2(g)  Fe2O3(s) H = -284 kJ
0
eq 2
Fe(s) + 2H+(aq)  Fe2+(aq) + H2(g) H0 = -86.2 kJ eq 3
0
and  H f [H2O(l)] = -285.8 kJ mol-1. (Answ: -103 kJ)
(DO NOT TAKE SHORT CUTS - YOU WILL LOOSE MARKS)
2 Estimate the combustion enthalpy of CH3OH(l) by using the appropriate average bond energies
data. Assume that the evaporation enthalpy of CH3OH(l) = 38 kJ mol-1 and that of H2O(l) = 44 kJ
mol-1. Use T = 298K (Answ: -692.8 kJ)
3 A system of 2 mol N2 gas is first heated at a constant volume from 98 to 198 K and then expanded
5R
isothermally from a volume of 10 L to a volume of 30 L. Assume CP  and that the gas is
2
ideal. Calculate H, q, w and U for the process. Assume that N2 has ideal gas behavior and that
both processes are reversible. (Answ: 4157 J, 6111.2 J, -3617.0 J, 2494.2 J)
4 Calculate the amount of heat required to bring 2 mol of liquid water at 90°C to water vapor at
+110°C. Given: Cp(water) = 75.48 J K-1 mol-1, Hvap(water) = 2257.5 J g-1,
Cp(water vapor) = a + bT + cT-2, a = 30.5 J K-1 mol-1, b = 0.0103 J K-2 mol-1, c = 0 J K+1 mol-1
(Answ: 1509.6 J + 81315.2 + J 687.9 J = 83512.7 J)
5 A system of 5 mol of an ideal gas is compressed isothermally at 300 K from 25L to 5L
a) under reversible conditions
b) at a constant external pressure of 5 atm
Calculate for both processes (i) the work w done and (ii) the change in pressure P.
(Answ: (a) 20.071 kJ, 1995.360 kPa (b) 10.133 kJ, 0 Pa)

Self-study: Mortimer page 91: problems 2.33, 2.34, 2.48, 2.55, 2.56:
2.33 (given a=0.3640 Pa m6 mol-2 and b = 4.267 x 10-5 m3 mol-1, answ: (b) 3506.9 J (c) 1520 J)
2.34 (given Cp(water) = 75.48 J K-1 mol-1, Hfus(water) = 333.5 J g-1, Hvap(water) = 2257.5 J g-1 answ:
54.217 kJ)
2.48 (Note: Consider the process in three steps: 1st heating of steam from 95°C to 100°C,
2nd condensation of steam at 100°C and 3rd the cooling back to 95°C.
Given Cp(water) = 75.48 J K-1 mol-1, Hvap(water) = 2257.5 J g-1, Cp(water vapor) = a + bT,
a = 30.5 J K-1 mol-1, b = 0.0103 J K-2 mol-1, answ: -40863.4 J mol-1)
2.55 (use table p 27, answ: (a) -2794 kJ mol-1 (b) -2855.68 kJ mol-1 (298 K), -2852.74 kJ mol-1 (373 K)
2.56 (a-d) (answ: (a) 303.14 K (b) 351.25 K (c) 400 K (d) -2013.23 J for (a), -1013.27 J for (b),
0 (for (c)).

26
TABLES OF SELECTED THERMODYNAMIC FUNCTIONS.

Table of selected thermodynamic functions and bond energies

Termodinamiese funksies by 298K / Bindingsenergieë/ kJ mol-1 /

Thermodynamic functions at 298K Bond Energy /kJ mol-1
0 0 0
H f / S / Cp/
kJ mol-1 J K-1 mol-1 J K-1 mol-1
CH4(g) -74.9 186.251 35.639 Br-Br 193 H-Br 366
C2H2(g) 226.731 200.958 44.095 C-C 343 H-Cl 432
C4H4(g) 52.467 219.33 42.886 C=C 615 H-F 568
C2H6(g) -84.68 229.6 52.63 CC 812 H-H 436
CO2(g) -393.522 213.795 37.129 C-Cl 3265 H-I 298
CaCO3(cr) -1206.92 92.9 81.88 C-F 490 H-N 391
CaO(cr) -635.089 38.212 42.12 C-H 416 H-S 367
H2(g) 0 130.68 28.836 C-N 290 N-N 160
H2O(g) -241.826 188.834 33.59 CN 891 NN 946
H2O(l) -286 69.95 75.351 C-O 351 N-O 176
N2(g) 0 191.609 29.124 C=O 724 O-H 464
NO2(g) 33.095 240.034 36.874 C=O (in CO2) 799 O-O 144
N2O4(g) 9.179 304.376 77.256 Cl-Cl 326 O=O (in O2) 498
O2(g) 0 205.147 29.376 F-F 158
C6H12O6(s) -1274 - -
C2H5OH(l) -277.67 160.7 111.46
C(s) 0 5.740 8.517
cr = crystalline

Table of selected enthalpy change for fusion and evaporation and molar heat capacities (T =
temperature in K)

Stof / Substance Hsmelt /Hfuss Hverdamp/Hvap Stof / Substance C P / JK-1mol-1

H2O 333.5 J g-1 2257.5 J g-1 H2O(g) 30.5+0.0103T
H2O 6.01 kJ mol-1 40.67 kJ mol-1 H2O(l) 75.48
CH4 58.41 J g-1 555.19 J g-1 H2O(s) 33
CH3CH3 95.10 J g-1 520.32 J g-1 CH4(g) 23.6+0.04786T-
0.000018T -2
CH3CH2OH 109.0 J g-1 878.58 J g-1 CH3CH3(l) 68.6
CO2 180.7 J g-1 526.6 J g-1 CO2(g) 44.2+0.00879T-
0.0000862T -2
CO 29.8 J g-1 240.98 J g-1 CO(g) 28.4+0.00419T-
0.0000046T -2
CO(l) 60.7
NOTE units: Hfuss (water) = 333.5 J g = 6.01 kJ mol
-1 -1

27
 6 SECOND LAW OF THEMODYNAMICS (Mortimer p 94-95, 102, 106-119)

6.1 Spontaneous and non-spontaneous processes

A spontaneous process is a physical or chemical change that occurs by itself.
E.g. the rolling of a rock downhill
heat-flow from a hot object to a cold one
C(s) + O2(g)  CO2(g) + heat

If these processes were to go in the opposite direction, they would be non-spontaneous:

work is needed to roll the rock back uphill
a heat-pump or a refrigerator is needed to make heat flow from a cold to a hot object
CO2(g) + heat  C(s) + O2(g)

Thus heat or work is needed to reverse a spontaneous process. This heat or work is obtained from
another spontaneous process. Consequence: The spontaneous processes in the universe are getting
less. Energy is less available for work. The term entropy is used to describe the depletion of
spontaneous processes in the universe. The total entropy of a system and its surroundings increases for
a spontaneous process. During a spontaneous process, the disorder of a system increases. Entropy S
is a thermodynamic function that describes the randomness or disorder of a system. The larger the
value of the entropy, the larger the degree of randomness or disorder and, therefore, the larger its
statistical probability.

(a) If water molecules are

dropped into a
container, they would
not expect to land in just
the right places to give a
highly ordered structure.
The way they landed is
low high determined purely by
entropy entropy chance; the disordered
liquid is more likely to
occur.
(b) Tossing bricks into the
air is more likely to give
a pile of bricks than a
brick wall.

6.2 Entropy (p 94-95)

Entropy, S, is a thermodynamic function that is a measure of the randomness or disorder of a system.
Symbol: S. S.I. unit of S is J/K. S is a state function: S = S(V, T, n). dS is an exact differential;
S depends only on the initial and final state of a system; S = Sf - Si =  dS (path independent).
C

REMEMBER: exact differential in CEM 214 (Thermodynamics) : dP, dV, dU, dH, dS.

28
6.3 The second law of Thermodynamics.
The first law deals with the conservation of energy. The second law is based on experimental fact. It
deals with the direction of spontaneous processes.
Verbal statement of second law: Kelvin: it is impossible for a system in a cyclic process to turn heat
completely into work. Clausius: heat cannot flow spontaneous from a cooler object to a hotter object
if nothing else happens. Entropy: The total entropy of a system and its surroundings always increases
for a spontaneous reaction.
Mathematical statement of second law: (p 102, 106-110)
dq rev
dS rev  for a reversible process (continuous state of equilibrium)and
Tsystem

dqirr
dS irr  for a irreversible process (spontaneous process)
Tsurr

6.4 S for different processes.

6.4.1 Adiabatic process (dq = 0) (p 106-109)

dqrev
reversible process: S rev   dS rev   0
T
S adiabatic  0
dq
irreversible process: Sirr   dSirr   irr  0 gives S irr  0
Tsurr

6.4.2 Non-adiabatic process

adiabatically
isolated

system
 dq
surrounding dSnon-adiabatic 
Tsurr

universe

Consider a system and its surroundings adiabatically insulated from the rest of the universe:
dScombination = dSsyst + dSsurr  0.
- dqsurr  dqsyst  dq
reversible process: dSsyst + dSsurr = 0 gives dSsyst = -dSsurr =  
Tsurr Tsurr Tsurr

 dq
irreversible process: dSsyst + dSsurr > 0 gives dSsyst > (similar to above).
Tsurr
29
6.4.3 Suniverse
Consider a system with its surroundings adiabatically insulated from the rest of the universe. It follows
similar as above, that dScombination = dSsyst + dSsurr  0. Since the combination is only part of the
universe involved in the process, the entropy of the universe cannot decrease: Suniverse  0. For a
reversible process Suniverse = 0.
Suniverse  0

6.4.4 General working equation for closed systems (p 110)

For any process that begins at an equilibrium state 1 and ends at an equilibrium state 2, the entropy
change is given by S = S2 - S1 =  dS . The actual process does not have to be a reversible process, as
C

long as it has equilibrium initial and final states, but the path on which the line integral is calculated,
must correspond to a reversible process. From the mathematical definition it follows:
dqrev
S rev   (closed system)
C T

6.4.5 Isothermal process (T = constant) (p 111)

1
T C
(i) S rev  dq rev

V2
(ii) Derivation of S  nR ln :___________________for a isothermal, reversible process, ideal gas
V1
Note:
 We can use (i) above, even if the T changes during the process and even if the process is
irreversible, as long as the final temperature = initial temperature. However, we must use qrev for
the isothermal reversible process in the formula and not the value of q for the actual process if it
differs from qrev.
 Since S is a state function, the above equation applies to any process of an ideal gas that begins and
ends at equilibrium states at the same T , even if the T varies during the process and even if the
process is irreversible!!!

6.4.6 Reversible phase changes (p 112)

H
Derivation of S  :______________________
T

6.4.7 Reversible changes in temperature (p 113)

T2
C P dT
a) T changes, P constant: Derivation of S  
T1
T
:______________________

T2
CV dT
b) T changes, V constant: Derivation of S  T T :______________________
1

30
6.4.8 S for irreversible processes (p 114-117)
Each irreversible process must be analyzed individually. Many of the irreversible processes that we
discuss begin with the system in one equilibrium or metastable state and ends with the system in
another equilibrium state. Because entropy is a state variable, we can calculate the entropy change of a
system using a reversible process having the same initial and final states as the irreversible process.

If the entropy change of the surroundings is required, a separate calculation is necessary because the
final state of the surroundings will not necessarily be the same in the reversible process as in the
irreversible process.
1 mol H2O(l) irreversible 1 mol H2O(s)
268.15 K process 268.15 K
Remember for irreversible process: Sirr for freezing of
 Suniverce > 0 supercooled liquid
 Calculate Ssyst and Ssurr separately S1 S3 water at -5°C to ice
at -5°C
1 mol H2O(l) S2 1 mol H2O(s) = S1 + S2 + S3
273.15 K 273.15 K = -21.23 J/K/mol

6.5 Examples on calculating S.

1) Given Hvapp(CCl3)= 43,0 kJ/mol for the evaporation process of CCl3 at 25 °C. Determine
Svapp(CCl3) at 25°C. (ANSW: 144 J/K/mol)
2) Calculate S and Ssurr for the reversible heating of 3 moles of liquid water from 30°C to 40°C
C
at constant pressure of 1 atmosphere. Given: Cp (liq water) = 75.48 J mol-1K-1 = P .
n
(ANSW: 7.35 J/K; -7.35 J/K)
3) 4.09 mole ideal gas expands from 10 L to 100 L at a constant temperature of 25°C. Calculate
q, w, U, S, Ssurr, Suniverce, P.
a. if it is a reversible expansion (ANSW: 23332 J; -23332 J; 0; 78.29 J/K; -78.29 J/K; 0, -
911 kPa)
b. if it is a irreversible expansion at constant external pressure of 1 atm (ANSW: 9119 J; -
9119 J; 0; 78.29 J/K; -30.6 J/K; 47.7 J/K, 0)
c. if the gas expands into vacuum (that means Pext = 0, an irreversible process!). (ANSW:
0 J; 0 J; 0; 78.29 J/K; 0; 78.29 J/K, 0)
4) 1 Kg of ice at -10°C is heated to water vapour at 100°C. Determine S. (Note: 4 processes!)
Given:  H vap (liquid water) = 40.67 kJ mol-1,  H fuss (ice) = 6.01 kJ mol-1,
CP (ice) = 33 J mol-1 K-1, CP (water) = 75 J mol-1 K-1. (ANSW: 8649.39 J/K)
5) One mole of supercooled liquid water at –5°C freezes to ice in a well-isulated vessel at a
temperature of –5°C. Calculate the entropy change of the water. Given CP (ice) = 33 J mol-1
K-1, CP (water) = 75 J mol-1 K-1,  H fuss (ice) = 6.01 kJ mol-1. (ANSW: -321.23 J/K)

31
Example on reversible and irreversible isothermal expansion of an ideal gas (for self-study)
n mole ideal gas expands isothermal from V1 to V2. Calculate q, w, U, S, Ssurr, Suniverce, P (a) if it is a reversible expansion (b) if it is a irreversible
expansion at constant external pressure of 1 atm (c) if the gas expands into vacuum (that means Pext = 0, an irreversible process!).
(a) reversible expansion (b) irreversible expansion (c) expands into vacuum (irreversible)
nRT Pext = 1 atm Pext = 0
Pext = Pint == ( for ideal gas )
V
(U)T = 0 = q + w (U)T = 0 = q + w (U)T = 0 = q + w
wsystem,reversible = w =  dw   (  Pext dV ) wsystem,irreversible = w =  dw   (  Pext dV ) wsystem,irreversible = w =  dw   (  Pext dV )
 nRT w =  Pext  dV   Pext ( V2  V1 ) w =  Pext  dV   Pext ( V2  V1 )
V2
V2
=  (  Pint dV )   V dV   nRT ln
V1
V1
qsystem,reversible = q = -w qsystem,irreversible = q = -w qsystem,irreversible = q = -w

dqsystem ,rev qsystem ,rev S system ,irreversible  S system ,reversible S system ,irreversible  S system ,reversible
S system ,reversible   
C
T T IF the initial and final states are the same IF the initial and final states are the same
(answer the same as in (a)) (answer the same as in (a))
Suniverse = Ssystem + Ssurroundings Suniverse = Ssystem + Ssurroundings Suniverse = Ssystem + Ssurroundings
Suniverse = 0 Suniverse > 0 Suniverse > 0
Ssurroundings = -Ssystem,reversible dq surroundings  dq system ,irreversible  S surroundings  
dq surroundings

 dq system ,irreversible 
S surroundings   
C
T C
T C
T C
T
Suniverse = 0 Suniverse = Ssystem + Ssurroundings > 0 Suniverse = Ssystem + Ssurroundings > 0
 P   P   P   P  P = 0 P = 0
dP    dV    dn    dT    dV
 V  n ,T  n V ,T  T  n ,V  V  n ,T
 P    nRT 
V2

P   dP     dV   V   dV
 V  n ,T V1
V  n ,T

 
V2 V2
1
 nRT    dV  nRT   V  2 dV
V1
V  V  n ,T V1

 1 1
V2
 1 
 nRT ( )  nRT   
 V  V1  V2 V1 
32
6.6 Entropy for the mixing of gasses (p 117-119)
Derivation of the entropy change of mixing of a mixture of ideal gasses
n
S   R  ni ln X i : _______________________________________
i 1

Example:
16 g methane (CH4(g)) and 32 g helium (He(g)) is mixed. Calculate the entropy of mixing.
Given: Atomic mass C=12, H=1, He=4 (ANSW: 26 J K-1)

6.7 Self-study and homework

Self-study: Examples 3.1, 3.3, 3.4, 3.5, 3.6, 3.8.
Exercise 3.6 (40.143 JK-1, -40.143 JK-1), Exercise 3.7 (88 kJ, 88kJ, 250 JK-1),
T nc 1 1
Exercise 3.8 ( S  na ln 2  nb(T2  T1 )  ( 2  2 ) ),
T1 2 T2 T1
3R
Exercise 3.9 (Assume Ag is an ideal gas, C v  , 24.31 JK-1)
2
Homework: Exercise 3.6 (assume ideal gas) and 3.7

7 COMBINATION OF THE FIRST AND SECOND LAW

7.1 Entropy change, S, in terms of volume and temperature.
Determination of entropy change, S during the heating of n moles of an ideal gas from volume V1 at
temperature T1 to volume V2 at temperature T2, by using the first and second laws of thermodynamics.

First law: dU = dq + dw = TdS - PdV (i)

dq
Second law: dS  (ii)
T
(ii) in (i): dU = dq + dw = TdS - PdV (iii)
dU P nC V dT nRdV
From (iii): dS   dV  
T T T V
T V
Thus: S   dS  nC V ln 2  nR ln 2
C T1 V1

7.2 Entropy change, S, in terms of pressure and temperature.

Determination of entropy change, S during the heating of n moles of an ideal gas from pressure P1 at
temperature T1 to pressure P2 at temperature T2, by using the first and second laws of thermodynamics,
as well as the definition of enthalpy, H.

dq
Second law: dS  (i)
T
First law: dU = dq + dw = TdS - PdV (ii)
Definition H: H = U + PV
Thus dH = dU + PdV + VdP = (TdS - PdV) + PdV + VdP = TdS + VdP (iii)
dH V nC P dT nRdP
From (iii): dS   dP  
T T T P
T2 P2
Thus: S   dS  nC P ln  nR ln
C T1 P1

33
8 THE THIRD LAW OF THERMODYNAMICS (Mortimer p 123-127)

8.1 The third law of thermodynamics

At absolute zero the entropy S of a perfectly pure crystalline substance is zero: S = 0 at T = 0 K.
T1
dq
The absolute entropy S of a system at temperature T1: S (T1 )   rev
0
T
Note:
 All perfect materials have the same entropy S at T = 0 K, viz. S = 0
 It is impossible to cool any system to 0 K.

8.2 Calculation of entropy S(T1) at constant pressure P.

General, if phase transitions occur:

C P ( liquid )dT H vap T C P ( gas )dT

T
C P ( solid )dT H fuss
T Tm g
dq
S ( T )   rev  0    
0
T T Tm Tm
T Tg Tg
T

If no phase transitions occur:

T
dq rew T C P dT
S( T )   
0
T 0
T

where: Tm = reversible melting temperature, Tg = reversible evaporation temperature

Hfuss = enthalpy change for fusion (melting), Hvap = enthalpy change for evaporation
Cp(s) = heat capacity for solid phase, s = solid, l = liquid, g = gas

Note: At low temperatures (<15K) C p  C v  aT 2  bT , a and b can be determined experimentally.

a b c d

Solid Solid Liquid Liquid Gas

T 0 113.74 113.74 261.44 261.44 K
S 0 68.46 108.39 201.06 282.52 J/mol/K
S 0 68.46 39.93 92.68 81.45 J/mol/K

Presentation of the entropy of C4H10 (isobutane). The crystal at 0 K is assumed to be perfect. Process
(a) is the rise in temperature from 0K to the melting point of 113.74 K (b) the melting (fusion) at
113.74 K (Hmelt = 4541 J/mol) (c) the rise in temperature from 113.74 K to the boiling point 261.44
K (d) evaporation at 261.44 K (Hvap = 21290 J/mol). Note how the entropy S in J/mol/K (disorder)
rises during each process.

34
8.3 Standard entropy S0
S0 of a solid or a liquid (gas) is the entropy of the substance (hypothetical ideal gas) at 298 K and P0 =
1 bar = 105 Pa. The unit of S0 is J mol-1 K-1. Values for S0 are tabulated.

The standard entropy change for a chemical reaction:

N


0
S0 =  S0(products) -  S0(reactants) = i S i (298K ) (example 3.11)
i 1

If the reaction we are working with corresponds to the formation of a compound from its elements,
then S0 we calculate is referred to as the standard entropy change of formation, S0f.

S0 are tabulated at 25°C (298 K). The above formula calculates S0 for reactions at 25°C. To obtain
entropy changes at other temperatures than 25°C:
T T
C P dT
S (T) = S (298K) +
0 0
 dS
298 K
= S (298K) +
0

298 K
T

with C P   i C P (i )   C P ( products)  C P (reaktants)

i

8.4 Examples on the third law

1) Calculate S0 for: CO(NH2)2(aq) + H2O(l)  CO2(g) + 2NH3(g) (354.8 J K-1)
2) Calculate S0f of H2O(l) at 25°C (-327 J K-1)
3) Calculate S0f of H2O(g) at 25°C (-88.8 J K-1)

4) Calculate S0 of H2O(g) at 200°C (Use CP (H2O(g)) = 34.5 J mol-1 K-1 at 386K, CP (H2(g) at
386K) = 28.9 J mol-1 K-1, CP (O2(g) at 386K) = 30.5 J mol-1 K-1; we use the constant value of
CP at the average temperature between 25°C and 200°C, ANSW -97.7 J K-1.

Homework: Examples on the third law paragraph 8.4 no 3) and 4).

Friendly advice when doing problems for homework, tests or exams:

DO NOT TAKE SHORT CUTS – SHOW ALL NESSESARY STEPS,
ELSE YOU MAY LOOSE MARKS!!!

35
9 SUMMARY OF SELECTED FORMULAS FROM THERMODYNAMICS
CHEM2613.
9.1 Work of expansion/compression
General expression dwsys = - Pext dV
Irreversible processes dwirr   Pext dV
Reversible processes dwrev   Pint dV (GAS LAWS may be used to calculate Pint)

9.2 Heat
V2
Isothermal process, ideal gas, reversible q T  nRT ln
V1
Constant volume (isochoric) process dqV  CV dT  dU
Constant pressure (isobaric) process dqP  CP dT  dH

9.3 Enthalpy
T2

Process in a closed system H   C P dT

T1

Heating a substance from T1 to T2 at constant P, with phase transitions

H  H s ( T1  Tm )  H melt  H l ( Tm  T g )  H vap  H g ( T g  T2 )
Tm Tg T2

  nC p ( solid )dT  n H melt   nC p ( liquid )dT  nH vap   nC p ( gas )dT

T1 Tm Tg

For chemical reactions

H o   i H o f (i )   H o
f (products)   H o
f (reactants) , i > 0 for products, i < 0 for
i prod react

reactants.
T2 T2

H (T2 )  H (T1 )   dH  H (T1 )   C P dT

T1 T1

with CP   iCP (i )   CP ( products)  CP (reac tan ts )

i

9.4 Entropy
dq rev
Second law for a reversible (equilibrium) process dS rev 
Tsystem

dqirr
Second law for an irreversible (spontaneous) process dS irr 
Tsurr

V2 P
Constant temperature (isothermal) reversible process, ideal gas S  nR ln  nR ln 2
V1 P1

T2
Constant pressure (isobaric) reversible process, ideal gas S  nC P ln
T1

T2
Constant volume (isochoric) reversible process, ideal gas S  nC V ln
T1
36
 T2 V T P
Ideal gas S   dS  nC V ln  nR ln 2 and S   dS  nC P ln 2  nR ln 2
C T1 V1 C T1 P1

H
Reversible phase changes S 
T
T2
C P dT
Reversible changes in temperature, P constant S  
T1
T
T2
CV dT
Reversible changes in temperature, V constant S  
T1
T
Absolute entropy when heating and phase transitions occur:

C P ( solid )dT H fuss g C P ( liquid )dT H vap T C P ( gas )dT

T Tm T
dq
S ( T )   rev  0    
0
T T Tm Tm
T T g Tg
T

Standard entropy change for a chemical reaction

N


0
S0 (298K) =  S0298K(products) -  S0298K (reactants) = i S i (298K )
i 1
T T
C P dT
S0(T) = S0(298K) +  dS
298 K
= S0(298K) + 
298 K
T
with C P   i C P (i )   C P ( products)  C P (reaktants)
i

37
WORKING SCHEDULE Thermodynamics CHEM2613
Textbook: Physical Chemistry by RG Mortimer

Lecture 1: Background (p 1-14, 34, 49)

Homework: Exercise 1.2 (b), 1.16 and the problem in 1.9 of these notes.
Lecture 2: Work and change in pressure (p 43-52)
Self-study: Example 2.1, 2.2 and 2.3
Homework: Exercise 2.1, 2.2b and 2.3a and b.
Lecture 3: Heat and internal energy (p 52-70), Note: possible classtest next lecture.
Self-study: Example 2.5, 2.6, 2.7a, 2.9, 2.12, exercise 2.12.
Lecture 4: Possible classtest (work, change in pressure, heat), p 74-77, Examples on U, q and w.
Self-study p 74-77, Example 2.13, 2.14, 2.15, 2.16
Lecture 5: Thermochemistry: Enthalpy H and internal energy U (p 77-90), Note: possible classtest
next lecture.
Homework: example 7 of paragraph 5.6 of this notes.
Self-study Example 2.17, 2.18, 2.19, 2.21, 2.23
Lecture 6: Possible classtest (chapter 2) and Examples on chapter 2.
Lecture 7: The second law (p 94-5, 102, 106-117)
Homework Exercise 3.6 (assume ideal gas) and 3.7
Lecture 8: Entropy for the mixing of gasses, examples on S (p 117-119), possible classtest next
lecture.
Lecture 9: Possible classtest (second law), Combining the 1st and 2nd law, the third law, examples
(p123-7)
Homework: Examples on the third law, paragraph 8.4 no 3) and 4).

Electrical
energy
Nuclear Battery Battery Mechanical
energy Electrolysis Fuel cell energy
Muscle
Radiolysis Rockets
Pressure reactions
Cold fusion?
(e.g. graphite to diamond)
Chemical
energy
Endothermic Photochemistry
reactions (absorption)
Exothermic Photon
reactions emission
Thermal Electromagnetic
energy energy (light)

38