YAMBOGO UNIVERSITY

FACULTY OF SCIENCE
DEPARTMENT OF CHEMISTRY
BACHELOR OF SCINCE IN CHEMICAL
ENGINEERING
CHE: 215 PHYSICAL CHEMISTRY

TASK: GROUP COURSEWORK

GROUP FOUR; Write short notes about state and path functions, the
firstand second laws of thermodynamics
LECTURER: MR. GEODFREY MUHWEZI
DATE: 05/10/2016

GROUP MEMBERS:

NAME: REG NO: NAME: REG NO:

1) KINABEYO MOSES 15/U/137/CHD/GV 10) OWINY FRED 14/U/6040/CHD/PD

2) KIREMBEKA JOSEPH 14/U/134/CHD/GV 11) NABAJJA CALEB 14/U/6015/CHD/PD

3) OKUBAL DANIEL 14/U/137/CHD/GV 12) ONGOLE JOSEPH 14/U/6035/CHD/PD

4) GIMEI BENEDICT 14/U/132/CHD/GV 13) OTUKOL BEN 14/U/6039/CHD/PD

5) BARIGYE EDWARD 14/U/130/CHD/GV 14) EKWARA TONNY 14/U/5981/CHD/PD

6) SSENDAGIRE 14/U/6042/CHD/PD 15) KIWANUKA ECLAS 14/U/13348/CHD/PD

GRAHAM
7)OTIM INNOCENT 14/U/6038/CHD/PD 16) MATOVU FRANK 14/U/6081/CHE/PE

8) ODONG LEO CEASAR 14/U/6033/CHD/PD 17) ASEGA ROBERT 14/U/6059/CHE/PE

9) TAREMWA DEUS 14/U/6046/CHD/PD 18) LUWAGA JULIUS 14/U/6076/CHE/PE

STATE AND PATH FUNCTIONS
(i) State functions. State functions or thermodynamic variables are variables that
describe the momentary state of a thermodynamic system. Irrespective of the path
or process taken from initial state to final state, the total state of such variables is the
same. There are examples of quantities which do not depend on path. Among these
are; temperature, pressure, specific volume, internal energy, entropy enthalpy etc.
These properties do not depend on the past history of the substance or on the path
it has followed in reaching a given state. They depend only on the present conditions
however reached. The values of state functions can always be represented as points
on the graph, which suggests the synonymous term point function.
It should be noted that the differential of a state function is spoken of as an
infinitesimal small change in the property, and is not referred to as a quantity. The
integration of such a differential results in a finite difference between two values of
the property for example
p2 u2

∫ dp= p2 −¿ p 1=∆ p∧∫ du=u 2−¿ u1=∆ U ¿ ¿

p1 u1

The important mathematical property of such a differential is that any correct

expression for it in terms of the state variables (P, T etc.) must be exact.
ii)Path functions
For path functions, the path from an initial state to final state is crucial. Each part or
segment of the path to the final state is necessary to take into account. Two
important examples of path functions are heat and work. These two functions are
dependent on how the thermodynamic system changes from the initial state to the
final state.
These two functions are introduced by the equation
∆ U which reperesent s the change∈the internal energy of the system
∆ U =q+ w

If all the change of states of system are plotted and all the points are conned, then
the line joining the change of states of the system is called the path
 THE FIRST LAW OF THERMODYNAMICS

This is the law of energy conservation. The change in total energy of a system is equal
and opposite to the change in total energy of surroundings.

The first law applies to the system and surroundings, considered together and not,
ingeneral, to the system alone .In it’smost basic form, the first law may be written:

∆ (Energy of the system)+∆ (Energy of surroundings) =0 (i)

In the system, energy changes in various forms may occur, e.g., changes in internal
energy, Potential and kinetic energy of a system as a whole, all potential and kinetic energy
of some parts of a system. Likewise, the energy change of the surroundings may consist of
increases or decreases of energy in various forms. Energy is stored in its potential, kinetic
and internal forms. These forms reside with material objects and exist because of the
position, configuration and motion of water. The transformations of energy from one form
to another and the transfer of energy from place to place often occur through the
mechanisms of heat and work.

If the boundary of a system does not permit the transfer of matter between the
system and its surrounding, the system is said to be closed and its mass is necessarily
constant. For such a system all energy passing across the boundary between the system and
its surrounding is transferred as heat and work. Thus the total energy change of the
surrounding must be equal to the energy transferred to or from it as heat and work i.e.

∆ (Energy of surroundings)=±Q±W

The first term of equation (i) may be expanded to show energy changes in
variousforms. If the mass of the system is constant and if only internal, kinetic and
potential-energy changes are involved,

∆ (Energy of the system)=∆ U+∆ E ❑K +∆ E P

With these substitutions, Equation (i) becomes

∆ U+∆ E K +∆ E P=±Q±W (ii)

 Where∆ U ,∆ E K ,and ∆ E Prepresent changes in internal, kinetic and potential energy of
the system respectively. The signs to be used on the right hand side of Equation (ii) must
now be chosen. The usual convention is to regard a quantity of heat as positive when it is
transferred to the system from the surroundings. On the other hand, a quantity of work is
usually regarded as negative when it is transferred from the system to the surroundings.
With this understanding, Equation (ii) becomes

∆ U+ ∆ E K +∆ E P=Q-W (For open system) (iii)

In words, equation (iii) states that the total energy change of the system is equal to
the heat added to the system minus the work done by the system. This equation applies to
the changes which occur in a constant-mass system over a period of time.

Closed systems often undergo processes that cause no changes in external potential
or kinetic energy, but only changes in internal energy .For such processes, the first law
(Equationiii) reduces to

∆ U=Q-W (For closed system when∆ E K +∆ E P=0) (iv)

Equation (iv) applies to processes involving finite changes in the system. For
differential changes this equation is written:

dU =dQ−dW

Changes in internal energy

Internal energy is the energy contained within the system, excluding the kinetic
energy of the motion and the potential energy of the system as whole due to
external force fields.
It keeps account of the gains and losses of energy of the system that are accounted
for its internal state.

When matter transfer is prevented by impermeable containing walls, the system is

said to be closed.

Here the first law of thermodynamics states that the increase in internal energy is
equal to the total heat added plus the work done on the system by its surroundings.
If the containing walls pass neither matter nor energy, the system is said to be
isolated, then its internal energy cannot change. In a sense, the first law of
thermodynamics may be regarded as establishing the existence of internal energy.
 The internal energy is one of the two cardinal state functions of the state
variables of thermodynamics system.
The internal energy of a given state of a system cannot be directly measured.
It is determined through some convenient chain of thermodynamic operations and
thermodynamic processes by which the given state can be prepared, starting with
reference state which is customarily assigned a reference value for its internal
energy. Such a chain, or path, can be theoretically described by certain extensive
state variables of the system,
∆ U =Q+W

The internal energy U of a given state of the system is determined relative to that of
a standard state of the system; by accompany a change of state from the reference
state to the given state.
∆ u=∑ Ei
i

Where ∆ U denotes the difference between the internal energy of the given
state and that of the reference state.

It is impossible to calculate the total internal energy hence a convenient null

reference point may be chosen for the internal energy.
The internal energy is an extensive property. It depends on the size of the
system or on the amount of the substance it contain

When a closed system receives energy as heat, this energy increases the internal
energy.
A second mechanism of change of internal energy of closed system is the doing of
work on the system, either in mechanical form by changing pressure or volume or by
perturbation, such as directing an electric current through the system.
If the system is open, the third mechanism that increase the internal energy is
transfer of matter into system hence for an open system,
∆ u=Q+W + ∆ Umatter

For a totally isolated system, none of the mechanisms can increase the internal
energy hence the change in internal energy of such system is equal to a constant that
is.
∆ U = A constant

For ideal gas system, the internal energy changes may be described solely by
changes in the kinetic energy of the gas molecules. Kinetic energy is simply the
internal energy
 Example: If 1200 joules of heat are added to aSystem in energy state U 1, and
the system does 800 joules of work on the surroundings, what is the:
1. The energy change for the system, ΔUsys?
ΔU = U2– U1 = q + w
ΔU = 1200 J + (-800 J)
ΔU = 400 J
ΔU = + 400 J
2. The energy change of the surroundings,
ΔUsurr?
ΔUsurr = −400 J

3. The energy of the system in the new stateU 2?

ΔUsys=U2– U1

U2 =U1+ΔUsys

U2= + 400J
Application of the first law of thermodynamics to:

Closed system
 Work and heat may enter or leave a closed system across its boundary and
may also be stored in the system as internal energy.

 This is a system that allows exchange of heat and work across the system
boundaries but does not allow transfer of matter across the boundaries.
With matter excluded, the changes in internal energy are due to heat transfer “Q”
and due to work “W”. Mass is not exchanged. Hence change in internal energy will be
given;
 
∆ u=Q+W
Isolated system

 This is a system where there is no exchange of mass or energy within the

system and its boundaries
For a totally isolated system, none of the mechanisms can change the internal energy
hence the change in internal energy of the system is constant.
∆ u= Aconstant
Open system
 This is a system that allows the exchange of mass and energy with the
surrounding.
 If the system is open, the mechanism that increases the internal energy is
transfer of matter into system.
∆ u=Q+W + ∆ Umatter
 
Applications of the first law of thermodynamics to flow systems
 Turbines. Turbines are mechanical devices that convert the energy of the
working fluid to shaft work.
 Compressors. These use shaft work to pressurize gases
 Throttling machine. Throttling devices are constrictions or orifices which bring
about a drop in pressure. They work on an assumption that inlet enthalpy=out
let enthalpy
 Pumps. Like compressors, pumps use shaft work to pressurize the working
fluid.

Limitation of the first law of thermodynamics

The first law of thermodynamics does not tell us why a spontaneous reaction
proceeds in one direction. All it says is that in any transformation, the energy of the
universe (the system and the surroundings taken together) remains the same before
and after any change. What, then, determines the direction of spontaneous process?

SECOND LAW OF THERMODYNAMICS

The second law is based on the idea that there is a natural tendency of any system
that is not in equilibrium to move in a certain direction. Eg a leaning brick left to fall
on its own, shiny iron sheets turning rusty etc.

Spontaneous processes
The term “spontaneous change “refers to a change happening without any
continuing outside influences. (Spontaneous change is a process that has a natural
tendency to occur
All such processes that occur without external input of energy are called
spontaneous processes. The processes that are spontaneous in one direction are not
spontaneous in the other direction. Examples of spontaneous processes include;
icemelting at room temperature, heat flow from hot to cold region,the rusting of iron
etc. Spontaneity is associated with an increase in the randomness or disorder of the
system. This randomness is expressed by a thermodynamic property called entropy.

The second law of thermodynamics is an expression of the universal law of increasing

entropy.

The second law of thermodynamics states that in spontaneous changes, the

universe tends towards a state of greater disorder. Therefore, all physical and
chemical changes occur such that the total entropy of the universe increases,
∆ S universe = increases or ∆ Suniverse> 0
 ¿]

The entropy of an isolated system never spontaneously decreases. It increases

during the course of a spontaneous change. e.g. as a hot block of metal cools, the
entropy increases as energy spreads into the surrounding.
∆ Sisolated ≥ 0

Changes in entropy
Provided that the temperature is constant, the change in the entropy of a
qrev
system can be calculated from the following expression: ∆ S=
T
[ q rev signifiesthattheenergymustbetransferedreversibly ]
For a reversible transfer of energy as heat, the temperatures of the surroundings and
the system must be only infinitesimally different.

Example1
Calculate the entropy change for the reaction below at 25 ocgiven that the entropies
of N2 H2 and NH3 gases are 191.5, 131.0 and 193.0 J/(k-mol) respectively
2NH3 (g)  N2 (g) + 3H2 (g)
2NH3 (g) N2 (g)+ 3H2 (g)
Srxn= nSproducts mSreactants
= [(1) (191.5 J/K · mol) + (3) (131.0 J/K · mol)] - [(2) (193.0 J/K · mol)]
= (584.5 J/K · mol - 386 J/K · mol)
Srxn= 198.5 J/K · mol (Entropy increases)

Entropy Changes in the Surroundings

 A decrease in the entropy of the system is outweighed by an increase in the
entropy of the surroundings. The surroundings function as a heat source or
heat sink.
 In an exothermic process, the surroundings absorbs the heat released by the
system, and Ssurr increases. qsys< 0; qsurr> 0 and Ssurr> 0
 In an endothermic process, the surroundings provides the heat absorbed by
the system, and Ssurr decreases. qsys> 0; qsurr< 0 and Ssurr< 0
Example 2

a) Calculate the change in entropy in 1.0L of water at 0 o C when it absorbs 235J

of energy from a heater.
b) If the 1.0L of water is at 99oC, what is the change in entropy?
c) Explain any difference in entropy change

Solutions

a. 0 o C=( 0+273 )=273 K .

∆ H =235 J
qrev ∆ H 235 J
∆ S= = = =0.861 J / K
T T 273 K
b. 99 o C=( 99+ 273 )=372 K
qrev ∆ H 235 J
∆ S= = = =0.632 J /K
T T 372 K

c. The change in entropy is smaller for the water at higher temperatures because
the water molecules are already chaotic.
At low temperature, the same amount of heat transferred had a greater effect on
changes in entropy.

From this, we can conclude that;

 The disorder of a system is expected to increase when heat is added because the
additional; heat energy increases the thermal motion of the molecules. (heating
increases thermal disorder)

 The disorder of the system is also expected to increase when a given amount of
matter spreads into a greater volume or is mixed with another substance.
Entropy is therefore a measure of the disorder or randomness of a system

∆ S> 0 disorderincreases(favoursspontaneity )

∆ S< 0 disorderdecreases(doesnotfavourspontaneity)
 Applications of the second law of thermodynamics

The difference in the quality between the two forms of energy; heat and work is
the subject matter of the second law of thermodynamics. This difference is such
that work is readily transformed into heat energy even to an efficiency of 100%
by elimination of friction and other energy losses whereas no process can convert
heat completely into work. The joule’s experiment showed that energy in form of
heat cannot be completely converted to work; however, energy in form of work
can be completely converted to heat energy.

 Heat engines
According to Kelvin Planck statement, that is, no heat engine can produce a net
amount of work while exchanging heat with a single reservoir only, it shows that
the second law does not prohibit the production of work from heat energy but
defines the limit on the fraction of the heat that may be converted to work in any
cyclic process.
A heat engine expresses the efficiency of this transformation.
The heat engine is a thermodynamic system operating in a thermodynamic cycle
to which net heat is transferred and from which network is delivered.
 Heat pump
This is a thermodynamic system operating in a thermodynamic cycle that
removes heat from a low temperature body to a high temperature body
 Refrigerator

A refrigerator is a cyclic device that extracts heat energy from a low temperature
medium but does not transmit it to high temperature body

Other statements of the second law of thermodynamics

There are some other statements of the second law of thermodynamics and they
include;

 Entropy is a property of the state only. Its value for an isolated system can
never decrease
  There is a general tendency in nature for energy to pass from more available
to less available
 The state of maximum entropy is the most stable state for an isolated system
 It is impossible to transfer heat from a colder system to a warmer without
other simultaneous changes occurring in the two systems or their
environment
 In an adiabatic process, the entropy either increases or remains unchanged.
 The entropy of the universe tends to a maximum value, approaching zero for a
reversible process

REFERENCES
Introduction to Chemical Engineering Thermodynamics by J. Smith
An Engineering Approach to Thermodynamics by Yunus A.
Principles of chemistry by CHAWLA. H.M, P.L.SONI and M.S.BATRA