Thermodynamic Systems

• A thermodynamic system is a
collection of matter which has
distinct boundaries.
• OR
A real or imaginary portion of
universe which has distinct
boundaries is called system.
• OR
A thermodynamic system is
that part of universe which is
under thermodynamic study.
• Lagrange (Closed Systems)
Vs.
Eulero (Open Systems)

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 Definitions
• A system is the object or material(s) under study,
separated from its surroundings by some specified
boundary – in essence, some collection of atoms.
If neither matter nor energy crosses the boundary,
it is an isolated system.
• If only energy crosses the boundary, it is a closed
system.
If both energy and material cross the boundary, it is
an open system.

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 Thermodynamic process
* The transformation of a system between two states describes
a path, which is called a thermodynamic process.
* There are infinite paths to connect two states.

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Type of processes
1- Isothermal process ΔT = 0
2- Isobaric process ΔP = 0
3- Isochoric process ΔV = 0
4- Adiabatic process q=0
5- Cyclic process φ=0

Reversible and Irreversible Processes:

Reversible process:
Is a process which maybe reversed at any moment by changing an
independent variable by an infinitesimal amount.

Irreversible Process:
Is the process that will not reverse the system if any change has
happened on the system.
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Extensive Properties( variables):
The property which depends on the amount of the substance, such as : ( S, m, U, V,
G ….)

Intensive properties( Variables) :

The properties which are independent on the amount of substance, such as (
Temp, press, density, viscosity, chemical potential …)

State of a system at equilibrium:

Is defined by the collection of all macroscopic properties that are described by
state variable (P, n, T, V) and independent on the history of the system.

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Work – force applied over a distance against a load (e.g. foot-pounds, or
Newton-meters = joules)

W = F . dh dh : distance F: force
pex
P=

F = P. A dh
W = P . A. dL ΔV = A. dL
gas
Then W = P ΔV A
W = Pext. ( V2 – V1)

The ( +ve ) sign for work means the system achieved work on the
surrounding, such as gas expansion.
The (-ve) sign for work means the surroundings achieved work on the
system, such as gas compression in a cylinder. 6
1- Expansion work
W = - Pex dv ( work done by the gas)
Work against a constant external pressure

Pex = constant P1 = P2
P
W = - ∫ Pex .dV

= -Pex (V2 – V1) W

= - Pex ΔV
V1 V2

2- Free Expansion ( Expansion against vacuum )

Pex = 0

W = - ∫ Pex .dV

W= 0
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3- Isothermal Reversible expansion work
Pi
Pgas = Pex
P=nRT/V
W = - ∫ Pex .dV

W = - ∫ Pgas .dV Pf

for ideal gas Pgas = nRT/ V w

Volume
Vi Vf

If T = constant ( Isothermal) ( Isothermal reversible work )

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Example:
For evaporation of one mole of water at constant pressure at one atm and 100oC :
1- what is the work done 2- what is the change in internal energy?

1- V1 = Mwt / d = 18 ml = 0.018 lit V2 calculation according to STP

W = -Pex (V2 – V1 )

W = -1 ( 30.6 – 0.018)

W = - 30.6 lit.atm = 30.6 *24.2 cal = 741.4cal

2- ΔU = q + W

q = 540 * 18 g

ΔU = 9720 – 741.4
= 8979 cal

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Example :
what is the work of reversible expansion of a mole of ideal gas at (0oC) from ( 2.24 to 22.4)
??

Reversible and isothermal

V1 = 2.24
V2 = 22.4
T= 0oC = 273oK
W= ?

W= -1 x 1.987 x 273 ln 22.4/2.24

W = -1250 cal . Mol-1

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Ex: calculate the maximum work for a reversible expansion at constant temperature from an
initial volume of V1 to a final volume ( 10 V1) that will do 10000 cal of work, if the initial
pressure is 100 atm .
1- find V1
2- if 2 mole of gas their, what would be the temperature??

Wrev = 2.303 nRT log 10V1/V1

Wrev = 2.303 nRT
P1 V1 = nRT = Wrev / 2.303
100 x V1 = 10000 / 2.303
V1 = 1.78 lit

2- W = nRT ln V2/V1 = 2.303 nRT log 10 V1 /V1 = 2.303 nRT

RT = 10000/ 2x2.303
T = 1100 oK

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Heat ( q) – the energy that flows from a body at higher temperature to one at lower
temperature by virtue of the temperature difference.
Experiments have shown that every material has a characteristic heat capacity
per gram, or specific heat capacity
heat capacity ( C ) – amount of heat that is required to raise the temperature of the
system 1oC .

If ( C ) is known , then we can determine the amount of heat required to raise the
temperature of a constant mass of a system from ( T1 ) to ( T2) by:

q = C ( T1 – T2 ) = C ΔT

The unit of heat capacity is ( joul / mole. Kelvin)

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 1st Law of Thermodynamics
Law of conservation of energy
(Energy can not be destroyed nor created)

dE = q − W
positive q : heat added to system
positive W : work done by system
• statement of energy conservation for a thermodynamic system
• internal energy E is a state variable
• W, q process dependent

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Thus the first law may also be state as: the net energy change of a closed system is
equal to heat transferred to the system minus the work done by the system.

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Exact differentials:
If a system is taken along path ( for example by heating it ), U changes from Ui to Uf ,
and the overall change is the sum (integral) of all the infinitesimal changes along the
path:

ΔU = ∫ du the value of ΔU depends on the initial and final states of the system
but independent on the path between them. (Exact differential )
and ΔU is said to be ( state function) .

Units of energy are ( J, kj, cal, kcal)

1 j = 1kg.m2.S-2

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Heat Content ( Enthalpy) ( H ):
Is the thermal change at constant pressure. ( the amount of heat absorbed or emitted by
a reaction).

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 ∆H = ∆E + P ∆V + V ∆ P

at constant ( P ) ∆P = 0

∆H = ∆E + P ∆V
From first law of thermodynamics
∆E = q - w
∆E = q - P ∆V
So... q = E + P ∆ V

Substitute in the equation above :

∆H = qp At constant prerssure

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 dE = Cv dT

∫dE = ∫ Cv dT if Cv = constant , then

E2 – E1 = ΔE = Cv ∫ dT

ΔE = Cv ( T2 – T1 )

ΔE = Cv ΔT ( for n= 1 )

ΔE = n Cv ΔT ( for n moles)

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 dH = Cp dT

In the same way as for Cv :

when Cp is constant , then :

ΔH = n Cp ΔT

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The variation of heat capacity with temperature can sometimes be
ignored if the temperature range is small; this approximation is highly
accurate for a monatomic perfect gas (for instance, one of the noble
gases at low pressure). However, when it is necessary to take the
variation into account, a convenient approximate empirical expression
is:
Cp,m = a + bT + c
T2

The empirical parameters a, b, and c are independent of temperature

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Example :
Cp = a + bT + c T2 + …..

∫dH = ∫ n Cp dT n=1

H2 - H1 = n ( a + bT + cT2 ) dT

ΔH = ∫ a .dT + ∫ bT .dT + ∫ c T2. dT

= a ( T2 - T1) + b ( T 2 - T2 ) + c 3 3
( T2 - T1 )
2 1 3
2

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Example / What is the change in molar enthalpy of N2 when it is heated from 25°C to
100°C? Use the heat capacity information in Table 2.2-
Cp,m = a + bT + c
T2
Method The heat capacity ofN2 changes with temperature, so we cannot use eqn 2.23b (which
assumes that the heat capacity of the substance is constant). Therefore, for the temperature
dependence of the heat capacity, and integrate the resulting expression from 25°C to 100°C.

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Example : -
The equation for the molar heat capacity for n-butane is ( Cp 4.64 + 0.0558 T ).
Calculate the heat necessary to rise the temperature of 1 mole of the Butane from 25
to 300oC at constant pressure.

∫ dH = ∫ n Cp dT

H2 - H1 = ∫ ( 4.64 + 0.0558 T ) dT

H2 - H1 = 4.64 ( T2 – T1 ) + 0.0558/ 2 ( T22 - T12 )

ΔH = (4.64 (300 -25) + 0.0558/ 2 ( 5732 - 2982 ) = 7959 Cal mol-1

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The Molecular Interpretation of the Internal Energy
1- For ideal gas, the only energy is the translational kinetic energy of the molecules,
and it will be found that the energy of the model gas of N molecules is

2- for Real gas , total Energy = Transitional energy + Internal Energy

Real atoms and molecules are not structureless particles. Real atoms and molecules
have translational energy and electronic energy, and molecules also have rotational
and vibrational energy.

3- Internal Energy = Erot + Evib

So Etotal = Etrans + Erot + Evib
Etot = 3/2 RT + 1/2 RT + 1/2RT

4- Evib consist of two type, each contribute by 1/2RT , so 2 x 1/2RT = RT

5- For linear molecules, there are two axis of rotation, each contribute by 1/2RT
For non-linear molecules, there are three axis of rotation, each contribute by 1/2RT

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6- Internal energy = 3N – 3 N : no of atoms in the molecule

7- Evib = 3N – 5 -------------- ( for linear molecules )

Evib = 3N – 6 -------------- ( for non-linear molecules)

Example : calculate Cv for a linear diatomic molecule .

Etot = Etrans + Einternal

Etrans = 3 x 1/2 R T = 3/2 RT 1/2 R T for each axis

Erot = 2 x 1/2 RT = 1 R T 1/2 RT each axis( linear molecule have 2 axis of rotation)

Evib = (3 N – 5 ) x R T there are 2 types of vibrations ( 2 x 1/2 RT = R T)

Evib = (3 x 2 - 5 ) x RT = 1 R T

Etot = 3/2 RT + RT + RT

Etot = 7/2 RT Cv = dE / dT
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Cv = 7/2 R
Adiabatic changes
We are now equipped to deal with the changes that
occur when a perfect gas expands adiabatically. A
decrease in temperature should be expected: because
work is done but no heat enters the system, the
internal energy falls, and therefore the temperature
of the working gas also falls. In molecular terms, the
kinetic energy of the molecules falls as work is done,
so their average speed decreases, and hence the
temperature falls. The change in internal energy of a
perfect gas when the temperature is changed from Ti
to Tf and the volume is changed from Vi to Vf can be
expressed as the sum of two steps (Fig. 2). In the first
step, only the volume changes and the temperature is
held constant at its initial value. However, because the
internal energy of a perfect gas is independent of the
volume the molecules occupy, the overall change in
internal energy arises solely from the second step, the
change in temperature at constant volume. Provided
the heat capacity is independent of temperature, this
change is ΔE = Cv ΔT
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Because the expansion is adiabatic, we know that q = 0; because ΔE = q- w , it then
follows that ΔE = - w . Therefore, by equating the two values we have obtained for ΔE,
we see that
w = - Cv ΔT

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Example :- A system consisting of 2.000 mol of argon expands adiabatically and
reversibly from a volume of 5.000 L and a temperature of 373.15K to a volume of
20.00 L. Find the final temperature.
Assume argon to be ideal with CV equal to 3nR/2.

Example :- Find the volume to which the system of the previous

example must be adiabatically and reversibly expanded in order to
reach a final temperature of 273.15 K.

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Example: a sample of Ar at one atm press and 25oC expands reversibly and adiabatically from
(0.5 to 1 Lit). Calculate the final temperature and the work done during this expansion. Given
that the molar heat capacity of Ar= 12.48 J/K mol-1.
P1 =1atm T1 =25oC
Cv =12.48 T2 = ?
V1 =0.5 L V2 =1L

1) T2 =? 2) w = ? 3) ΔE

V1T1Cv/R = V2 T2Cv/R

T2 = ( V1/V2)R/Cv .T1

T2 = ( 0.5/1)1/1.5 x 298 = 188oK

For adiabatic process w = CvdT = Cv ΔT
PV=nRT
n = ( 1x 0.5) / (0.0821x298) = 0.02 mol

2) W = nCv ΔT = 0.02 x 12.48 x (188 – 298)

W = -27 j

3) ΔE = q – w
q=0
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ΔE = W = -27 J
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 Thermochemistry

The study of the energy transferred as heat during the course of

chemical reactions is called thermochemistry. Thermochemistry is a
branch of thermodynamics because a reaction vessel and its contents
form a system, and chemical reactions result in the exchange of energy
between the system and the surroundings. Thus we can use calorimetry
to measure the energy supplied or discarded as heat by a reaction, and
can identify q with a change in internal energy (if the reaction occurs at
constant volume) or a change in enthalpy (if the reaction occurs at
constant pressure). Conversely, if we know ΔU or ΔH for a reaction, we
can predict the energy (transferred as heat) the reaction can produce.

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 The Truth about Enthalpy

1. Enthalpy is an extensive property.

2. ∆H for a reaction in the forward
direction is equal in size, but opposite
in sign, to ∆H for the reverse reaction.
3. ∆H for a reaction depends on the state
of the products and the state of the
reactants.
Thermochemistry

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 Standard enthalpy changes
Changes in enthalpy are normally reported for processes taking place
under a set of standard conditions. In most of our discussions we shall
consider the standard enthalpy change, ΔHo, the change in enthalpy for a
process in which the initial and final substances are in their standard
states: The standard state of a substance at a specified temperature is its
pure form at 1 bar.

For example, the standard state of liquid ethanol at 298 K is pure liquid
ethanol at 298 K and 1 bar; the standard state of solid iron at 500 K is
pure iron at 500 K and 1 bar. The standard enthalpy change for a reaction
or a physical process is the difference between the products in their
standard states and the reactants in their standard states, all at the same
specified temperature.

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 Different types of Enthalpies of physical change
The standard enthalpy change that accompanies a change of physical
state is called the standard enthalpy of transition and is denoted ΔtrsHo.
The standard enthalpy of vaporization, ΔvapHo, is one example. Another
is the standard enthalpy of fusion, ΔfusHo, the standard enthalpy change
accompanying the conversion of a solid to a liquid, as in

Because enthalpy is a state function, a change in enthalpy is independent

of the path between the two states. This feature is of great importance in
thermochemistry, for it implies that the same value of I'1H-e- will be
obtained however the change is brought about between the same initial
and final states. For example, we can picture the con- version of a solid
to a vapour either as occurring by sublimation (the direct conversion
from solid to vapour),

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 or as occurring in two steps, first fusion (melting) and
then vaporization of the result- ing liquid:

Because the overall result of the indirect path is the same as

that of the direct path, the overall enthalpy change is the
same in each case, and we can conclude that (for processes
occurring at the same temperature)

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 Hess's law
The standard enthalpy of an overall reaction is the sum of the standard
enthalpies of the individual reactions into which a reaction may be
divided.
The individual steps need not be realizable in practice: they may be
hypothetical reactions, the only requirement being that their chemical
equations should balance.

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Standard enthalpies of formation
The standard enthalpy of formation, ΔfHo, of a substance is the standard
reaction enthalpy for the formation of the compound from its elements in
their reference states. The reference state of an element is its most stable
state at the specified temperature and 1 bar. For example, at 298 K the
reference state of nitrogen is a gas of N2 molecules, that of mercury is
liquid mercury, that of carbon is graphite, and that of tin is the white
(metallic) form.
Standard enthalpies of formation are expressed as enthalpies per mole of
molecules or (for ionic substances) formula units of the compound. The
standard enthalpy of formation of liquid benzene at 298 K, for example,
refers to the reaction
6C(s, graphite) + 3H2(g) -- 7C6H6(l)
and is +49.0 kJ mol-I. The standard enthalpies of formation of elements
in their reference states are zero at all temperatures.

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