MODULE 2

CHE 216
Lecture 5:
1st
Law of
Thermodynamics
Part 1: Basics and Conventions
D EPA R T MEN T OF C H EMIC A L EN GIN EER ING
U N IVER SIT Y O F SA N TO TO M A S
M A N IL A , PH IL IPPIN ES

UST - DEPARTMENT OF CHEMICAL

1
ENGINEERING
Overview
Chapter 2 of Atkins: The First Law: Concepts
Sections 2.1-2.2 of Atkins (7th, 8th and 9th editions)
Sections 2.3-2.4 of Atkins (7th, 8th & 9th editions)
Basic Concepts : Work, Heat, Energy

The First Law of Thermodynamics - Conservation of Energy

Expansion Work
General Expression for Work, Free Expansion
Expansion Against Constant Pressure, Reversible
Expansion, Isothermal Reversible Expansion

Enthalpy

Heat Transactions: Heat Capacity

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 Thermodynamic Definitions
System: The object or region of
interest
Surroundings: Everything outside of
the system (we do our measuring in
the surroundings)

The definition of the system is very

dependent upon the boundaries
which separate the system the the
surroundings - i.e., can energy, which
is the capacity to do work, be
transferred between the system and
surroundings

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Thermodynamic Definitions
Open: Matter can go in and out of the system

Closed: Matter cannot go in and out of the system

Isolated System: Closed system with no thermal or mechanical

contact with the outside world (this is an ideal system)

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Thermodynamic Definitions
Energy: Capacity to do work - the energy of a system can be changed
by work and heat Units: joules (J) or for molar energy kJ mol-1

Work: A form of energy which can transfer in and out of a system, that
is stored in the organized motion of molecules. Work is done
when an object is moved against some opposing force
Heat: A form of energy which can
transfer in and out of a
system, that is stored in
the random motion
(thermal motion) of
molecules. If an energy
difference of a system
results from a temperature
difference between it and
its surroundings, energy
has been transferred as
heat Work Heat
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Thermodynamic Definitions of
Work & Heat
Work: Work (w) is energy which is transferred across the boundary of
a thermodynamic system during a change in its state and which
could be converted completely into the “lifting of a weight” in the
surroundings (i.e., motion of a mass against opposing force).
Sign conventions for work:
wsystem < 0 Work is done by the system on the surroundings.
wsystem > 0 Work is done on the system by the surroundings.

Heat: Heat (q) is energy which is transferred across the boundary of a

thermodynamic system during a change in its state by virtue of
a difference in temperature between the system and its
surroundings.
Sign conventions for heat:
qsystem < 0 Heat transferred from the system to the surroundings.
qsystem > 0 Heat transferred to the system from the surroundings.
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 SURROUNDING
Heat flow INTO Heat flow OUT
+q -q
SYSTEM
Internal
Work done ON Energy (U)
Work done BY
+w -w
e.g. compression e.g. expansion

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More About Heat
Diathermic (Diabatic) System: A
system in which energy is allowed
in and out in the form of heat -
system in thermal contact with
surroundings .

Adiabatic System: A system in

which heat is not allowed in or out

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More About Heat
(a) Endothermic Process:
Process that absorbs heat

(b) Exothermic Process:

Process that releases heat
(c)Endothermic
process in a
diathermic container:
decreases temperature
of surroundings

(d)Exothermic process
in a diathermic
container: increases
temperature of
surroundings
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Intensive vs. Extensive Property
Extensive property: is dependent upon the amount of matter
Properties whose values are increased/decreased in direct
proportion to the enlargement/reduction of the system

Intensive property is independent of the amount of matter -

all of the thermodynamic driving forces are selected from
among properties of this type.

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 Thermodynamic Functions
State Function Path Function
a property of a system that depends  a property of system that depends by
only on the state of the system. which the system achieved a particular
Pressure (P), Volume (V), state
Temperature (T), Enthalpy (H), Internal  work (w) and heat (q)
Energy (U), Gibbs Free Energy (G),  Path function is an inexact differential
𝑓𝑖𝑛𝑎𝑙
Entropy (S)
𝑞= 𝛿𝑞
State Function is an exact differential 𝑖𝑛𝑖𝑡𝑖𝑎𝑙,𝑝𝑎𝑡ℎ State 2: P V T
2 2 2
𝑓𝑖𝑛𝑎𝑙
∆𝑈 = 𝑑𝑈 = 𝑈𝑓𝑖𝑛𝑎𝑙 − 𝑈𝑖𝑛𝑖𝑡𝑖𝑎𝑙
𝑖𝑛𝑖𝑡𝑖𝑎𝑙

State 1: P1V1T1

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Internal Energy
Internal Energy total energy of a system at any given time - it
(U): comes from the total kinetic and potential
energy of molecules which compose the
system

Change in Energy Change in U as system goes from an initial

( U): state with energy Ui to final state with Uf
U = Uf - Ui

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 𝑈= 𝐾. 𝐸 + 𝑃. 𝐸
SYSTEM
Internal
Energy (U)
Kinetic Energy: Potential Energy:
Energy in Motion Stored Energy

KE = ½ mv2  Chemical
 Electrical
KE = ½ Kg (m/s)2  Nuclear
KE = ½ (Kg m/s2) (m)  Gravitational
KE = ½ N (m) Etc...
N m = Joule
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Conservation of Energy
Methods of
transferring energy

Heat (q)
SYSTEM
Internal SURROUNDING
Energy (U) Internal
Work (w)
Energy (U)

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 Changes in Internal Energy
Ufinal

U > 0
Internal Energy (U)

Internal Energy
Increases
Uinitial

U < 0
Internal Energy
Decreases

Ufinal
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Conservation of Energy
Internal energy of a system can be changed by:
1. Doing work to the system (w)
2. Energy transferred as heat to the system (q)

U = q + w
Heat and work are equivalent ways of changing the energy of a system
Recall:
If heat or work are transferred to the system:
q > 0, w > 0 (acquires energy)
If heat or work are transferred from the system:
q < 0, w < 0 (releases energy)

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 Methods of
transferring energy

Heat (q)
SYSTEM
Internal SURROUNDING
Energy (U) Internal
Work (w)
Energy (U)

Usystem= Uinitial – Ufinal Usurrounding =Uinitial – Ufinal

 Usystem = - Usurrounding

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1st Law of Thermodynamics
Energy cannot be created or destroyed,
only transformed or transferred

Transformation

Energy Energy
Before After

The Energy of the Universe Remains Constant

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Example 1
If an electric motor produced 15 kJ of energy each second
as mechanical work and lost 2 kJ of heat to the
surroundings, what is the change in internal energy?

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 General Expression for Work
 w = F dx
F F

w=0 w>0

Initial Initial
position position x > 0

Displacement is necessary for work to occur

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Work Done by an Expanding Gas
Pext
Work done on system

Pext w=-pV

dx

P1, V1 P2, V2

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P-V Work: Compression
Pext

Pext

P1, V1 P2, V2

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Example 2
A gas expands against a constant pressure of 200 kPa from
10 dm3 to 20 dm3. How much work was done by the gas?
Answer: -2.00 kJ

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Work Done by an Expanding
Gas
∆𝑈 =𝑞+𝑤
𝑤 = −𝑝 ∆𝑉
∆ 𝑈 = 𝑞 − 𝑝 ∆𝑉
Expansion work clearly depends on 𝑝 and ∆𝑉
Two ways to make expansion work = 0

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Free Expansion
∆ 𝑈 = 𝑞 − 𝑝 ∆𝑉
But in space (or vacuum
conditions) p =0

∆𝑈 =𝑞
Internal Energy is equal
to the heat supplied to
the system

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Reactions at Constant Volume
(Isochoric)
∆ 𝑈 = 𝑞 − 𝑝 ∆𝑉
At constant volume ∆𝑉 = 0

∆ 𝑈 = 𝑞𝑣
𝑞𝑣 = heat supplied at constant
volume

Constant volume reactors must

withstand massive pressures –
chemical industry

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Reactions at Constant Pressure
(Isobaric)
∆ 𝑈 = 𝑞 − 𝑝 ∆𝑉
∴ 𝑞𝑝 = ∆ 𝑈 + 𝑝 ∆𝑉 𝑎𝑡 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒
 Now we define a new-state function
𝐻 = 𝑈 + 𝑝𝑉
∴ ∆ 𝐻 = ∆𝑈 + ∆ 𝑝 𝑉
∆ 𝐻 = ∆𝑈 + p ∆V + V ∆𝑝
 But at constant pressure, ∆𝑝 = 0 hence, V∆𝑝 = 0
∴ ∆ 𝐻 = ∆𝑈 + 𝑝∆𝑉

∆ 𝐻 = 𝑞𝑝
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 Expansion Against
Constant Pressure
During expansion, external pressure pex is
constant (e.g., atmosphere)
𝑉𝑓
𝑤 = −𝑝𝑒𝑥𝑡 𝑉𝑖
𝑑𝑉 = −𝑝𝑒𝑥𝑡 𝑉𝑓 − 𝑉𝑖 = −𝑝𝑒𝑥𝑡 ∆ 𝑉

The integral above is interpreted as area, as we

watch work done by a gas expanding against a
constant pressure

The magnitude of work, *w*, is equal to the area

beneath the line with p = pex, between final and
initial volumes: p, V graphs to calculate
expansion are indicator diagrams

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Reversible Process
 If the external pressure is decreased by
infinitesimal amount, the gas expands and
performs work (w<0).

 If the external pressure is increased by an

infinitesimal amount, the is compressed and work
is done on the gas (w>0)

 When the condition Pext = P, the gas can undergo

two opposing processes, depending if the
pressure was increased by a very small amount.
This condition is described as reversible
condition.

 Under reversible condition, the gas performs

maximum work.
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 Irreversible Process
p  Suppose the external pressure
is dropped instantaneously to
P1 P2. The work done by the
system is now against pressure
P2. The work done in the
P2 expansion is:

𝑤𝑖𝑟𝑟𝑒𝑣 = −𝑃2 ( 𝑉2 − 𝑉1 )
T1
V
V1 V2
Reversible Isothermal
Expansion of an Ideal Gas
Ideal Gas EoS: pV = nRT or p = nRT /V
Consider a 1 mol of an ideal gas at 298 K,
p = ( 1 mol x 8.314 J mol-1 K-1 x 298 K ) / V
p = 2477.572 J / V
Bring out you calculators! Using the above equation ,
calculate the pressure of the gas for the following
volumes 1, 3, 5, 7 , 9 and 11 m3
Answers: 2478, 826,496,354,275, and 225 Pa respectively

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Isothermal Expansion

External pressure, p = 2478 Pa  Volume = 1 m3

Now imagine the external pressure suddenly
drops to 826 Pa. What happens to the gas?

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 Reversible Isothermal
Expansion of an Ideal Gas
2500.0
V(m3) P(Pa) Increment Work
1 2477.6
3
5
825.9
495.5
2
2
1652
991 2000.0
w = 1652 + 991 + 708 + 551 + 450
7
9
353.9
275.3
2
2
708
551 w = - 4352 J
Pressure (P/Pa)

11 225.2 2 450 1500.0

w = 4352

1000.0

w = p V
w = 826 (2)
500.0 w = (-)1652 J w = p V
w = 496 (2) w = p V
w = 354 (2) w = p V
w = (-) 991 J w = (-) 708 J w = 275.3 (2) w = p V
w = 225.2 (2)
w = (-) 551 J w = (-) 450 J
0.0
1 2 3 4 5 6 7 8 9 10 11
Volume (V/m3)

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 Reversible Isothermal
Expansion of an Ideal Gas
2500
V(m3) P (Pa) Increment Work
1 2478
2 1239 1 1239
3 826 1 826 2000
4 619 1 619
5 496 1 496
w=-5004 J
Pressure (P/Pa)

6 413 1 413
7 354 1 354 1500
8 310 1 310
9 275 1 275
10 248 1 248
11 225 1 225 1000

w=5004
500

0
1 2 3 4 5 6 7 8 9 10 11
Volume (V/m3)

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 Reversible Isothermal
Expansion of an Ideal Gas
V(m3) P (Pa) increment Work 2500
1 2478
1.5 1652 0.5 826
2 1239 0.5 619
2.5 991 0.5 496 2000
3 826 0.5 413
3.5 708 0.5 354
Pressure (P/Pa)
4 619 0.5 310
4.5 551 0.5 275 1500
5 496 0.5 248
5.5 450 0.5 225
w = - 5428 J
6 413 0.5 206
6.5 381 0.5 191 1000
7 354 0.5 177
7.5 330 0.5 165
8 310 0.5 155
8.5 291 0.5 146 500
9 275 0.5 138
9.5 261 0.5 130
10 248 0.5 124
10.5 236 0.5 118 0
11 225 0.5 113 1 1.5 2 2.5 3 3.5 4 4.5 5 5.5 6 6.5 7 7.5 8 8.5 9 9.5 10 10.5 11

w = 5428 Volume (V/m3)

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 Reversible Isothermal
Expansion of an Ideal Gas
2500
Allow the gas to
expand infinitesimally
2000 small amounts
Pressure (P/Pa)

1500 w = - 5941 J Work done Is the

1000
(Maximum work) shaded area!
 A process of infinitesimally
500 slow expansion would take
an infinitely long period of
0
time.
1 12  Reversible expansion work
Volume (V/m3) is only a theoretical, if
extremely useful construct

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w for Reversible Isothermal
Expansion
𝑤 = −𝑝 𝑑𝑉
𝑇ℎ𝑒 𝑖𝑑𝑒𝑎𝑙 𝑔𝑎𝑠 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛: 𝑝 = 𝑛𝑅𝑇 /𝑉
𝑤 = −(𝑛𝑅𝑇)𝑉 𝑑𝑉
𝑑𝑉
𝑤 = −𝑛𝑅𝑇
𝑉
𝑑𝑉
𝑤= −𝑛𝑅𝑇
𝑉
𝑓𝑖𝑛𝑎𝑙 𝑑𝑉 𝑉
𝑤 = −𝑛𝑅𝑇 𝑖𝑛𝑖𝑡𝑖𝑎𝑙 𝑉
= −𝑛𝑅𝑇 [ln 𝑉] 𝑉𝑓
𝑖

𝑤 = −𝑛𝑅𝑇 [ ln 𝑉𝑓 − ln 𝑉𝑖 ]
𝑉𝑓
𝑤 = −𝑛𝑅𝑇 ln
𝑉𝑖

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 Reversible Isothermal
Expansion of an Ideal Gas
𝑉𝑓
2500 𝑤 = −𝑛𝑅𝑇 ln
𝑉𝑖
2000 𝐽
𝑤 = −1𝑚𝑜𝑙 8.314 298 𝐾 ln 11
𝑚𝑜𝑙 𝐾
Pressure (P/Pa)

1500
w = - 5941 J 𝑤 = −5941 𝐽
1000 • Reversible expansion is
an infinitely slow
500 theoretical construct.
• Extremely useful as it
0 enables determination of
1 12
the maximum possible
Volume (V/m3) work that can be done by
an expanding gas.
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Example 3
One mole of argon gas at 0oC is expanded isothermally and
reversibly from a volume of 22.4 dm3 to 44.8 dm3. Calculate
w, q, △U and △H for this process.
Answers: -1.57 kJ, 1.57 kJ, 0 kJ, 0 kJ

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Example 4
64.0 g of oxygen gas at 27oC is expanded isothermally from
a volume of 22.4 dm3 to 44.8 dm3 against a constant
pressure equal to the final pressure of the gas. Calculate w,
q, △U and △H for this process.
Answers: -2.49 kJ, 2.49 kJ, 0 kJ, 0 kJ

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 Relation of Internal Energy
and Enthalpy †

For a perfect gas, the internal energy and enthalpy can be related by
H = U + pV = U + nRT

For a measureable change in enthalpy:  H =  U +  n gas RT

where  n g a s is the change of moles of gas in the reaction.

For instance: 2H2(g) + O2(g)  2H2O(l)  n g a s = -3 mol

3 mol of gas are replaced by 2 mol of liquid, so at 298 K
 H -  U = - ( 3 m o l ) x RT = - 7.5 kJ
Why is the difference negative?
Heat escapes from system, during reaction, but the system contracts as the
liquid is formed (energy is restored from the surroundings)

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Heat
Heat (q): a measure of thermal energy transfer that
can be determined by the change in the
temperature of the object

Heat flow INTO Heat flow OUT

+q System -q

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Heat
Factors that determine amount of heat
transfer:
 Temperature Change
 Amount of substance
 Nature of the substance

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Heat Capacity

Heat Capacity, C, is the heat energy required to

raise the temperature of an object by 1oC or 1K
𝑞
𝐶=
∆𝑇

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Heat Capacity
Heat capacity is an extensive property:

Two ways to make Heat capacity intensive property:

Specific Heat Capacity, Cs = C / m units J K-1 Kg-1

Molar Heat Capacity, Cm = C / n units J K-1 mol-1

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Isochoric Heat Capacity
Isochoric heat capacity is
defined as:

𝑞𝑣 ∆𝑈
𝐶𝑣 = =
∆𝑇 ∆𝑇
∂𝑈
𝐶𝑣 =
∂𝑇 𝑉
The heat capacity at temperature A
is lower than that at temperature B

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Isobaric Heat
Capacity
Isobaric heat capacity is
defined as:
𝑞𝑝 ∆𝐻
𝐶𝑝 = =
∆𝑇 ∆𝑇

∂𝐻
𝐶𝑝 =
∂𝑇 𝑃
The heat capacity at temperature A
is lower than that at temperature B

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Cp,m and Cv,m Relationship for
Ideal gas
𝐻 = 𝑈 + 𝑝𝑉
𝐻𝑚 = 𝑈𝑚 + p 𝑉𝑚
For Ideal Gas pV = nRT or pVm = RT
𝐻𝑚 = 𝑈𝑚 + 𝑅𝑇
For a change in Temperature
The isobaric molar heat capacity of an
∆𝐻𝑚 = ∆𝑈𝑚 + 𝑅∆𝑇 ideal gas is greater than its isochoric molar
Dividing both sides by ∆𝑇 heat capacity by 8.314 joules per kelvin per
mole
∆𝐻𝑚 ∆𝑈𝑚
= +𝑅
∆𝑇 ∆𝑇
∆𝐻𝑚 ∆𝑈𝑚
− = 𝑅 𝑜𝑟 𝐶𝑝,𝑚 − 𝐶𝑣,𝑚 = 𝑅
∆𝑇 ∆𝑇

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Variations and Relations of Heat
†
Capacities
Variation of heat capacity is negligible for small temperature
ranges - good for noble gases - however, if accurate treatment is
necessary
𝑐
𝐶𝑝,𝑚 = 𝑎 + 𝑏𝑇 + 2 a b/(10-3K-1) c/(105K2)
𝑇
Graphite 16.86 4.77 -8.54
CO2(g) 44.22 8.79 -8.62
where a, b and c are H2O(l) 75.29 0 0
empirical parameters N2(g) 28.58 3.77 -0.50
independent of T

At constant pressure, most systems expand when heated, and do

work on the surroundings while losing internal energy, with some
energy supplied as heat leaking back into the surroundings.

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 Dependence of Heat Capacity
on Pathway
Solids and liquids
𝐶𝑝 ≈ 𝐶𝑣

Ideal Gases:
𝐶𝑝,𝑚 − 𝐶𝑣,𝑚 = 𝑅

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 Why is Cp > Cv
Constant Volume Process Constant Pressure Process
Expansion
work

q q Increase T
Increase T

All energy inputs goes to increase All energy inputs goes to increase
the temperature only! temperature and expansion work!

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Example 5
Two moles of helium gas at 273 K and 400 kPa are heated
reversibly to 373 K at constant pressure. Calculate w, q, △U
and △H for this process.
Answers: -1.66 kJ, 4.16 kJ, 2.49 kJ, 4.16 kJ

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Example 6
Two moles of helium gas at 273 K and 400 kPa are heated
reversibly to 373 K at constant volume. Calculate w, q, △U
and △H for this process.
Answers: 0 kJ, 4.16 kJ, 2.49 kJ, 4.16 kJ

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Assessment 1
How much work is done if 240 L of argon gas
irreversibly double in volume against 1 bar of
pressure?
A) 240 J
B) 2.4 kJ
C) 24 kJ
D) 240 kJ

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Assessment 2
An exothermic reaction releases 146 kJ of heat energy and
3 mol of gas at 298 K and 1 bar pressure. Which of the
A) ΔU=−138.57
following kJ and is correct?
statements
ΔH=−138.57 kJ
B)
ΔU=−153.43 kJ and ΔH=−153.43 kJ
C)
ΔU=−138.57 kJ and ΔH=−146.00 kJ
D)
ΔU=−153.43 kJ and ΔH=−146.00 kJ

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Assessment 3
4.4 kg of carbon dioxide gas, CO2​, undergo isothermal
expansion at 298 K from a volume of 2 to 5 m3 in three steps
of 1 m3.Assuming ideal gas behaviour, what is the total work
A)
performed by the gas?
194 kJ
B)
245 kJ
C)
387 kJ
D)
461 kJ

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Assessment 4
4.4 kg of carbon dioxide gas, CO2​, undergo reversible
isothermal expansion at 298 K from a volume of 2 to 5 m3.
Assuming ideal gas behaviour, what is the total work
performed
A) by the gas?
138 kJ
B)
227 kJ
C)
294 kJ
D)
362 kJ

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Assessment 5
How much expansion work is done on the system when
exactly 1 mol of solid ammonium chloride, NH4​Cl, decomposes
completely to yield gaseous ammonia, NH3​, and hydrogen
chloride, HCl, at a temperature of 1280 K. Treat the expansion as
irreversible and the gases formed as perfect.

A) -21.3 kJ
B) -39.1 kJ
C) -47.3 kJ
D) -52.8 kJ

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Assessment 6
The molar heat capacity of solid aluminium is 24.4 J K−1 mol−1 at 25∘C.
What is the change in internal energy when 1 mol of solid aluminium is
heated from a temperature of 20∘C to 30∘C?

A) 102 kJ
B) 128 kJ
C) 153 kJ
D) 244 kJ

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Assessment 7
In the calibration step of a thermochemistry experiment, a current of
124 mA, from a 24.0 V source was allowed to flow through the electrical
heater for 219 s and was found to result in an increase in the
temperature of the calorimeter and its contents of +1.39 K. Given that
the energy supplied by an electrical circuit is the voltage multiplied by
the current, multiplied by the time, what is the heat capacity of the
calorimeter and its contents?

A) 194 JK-1
B) 322 JK-1
C) 469 JK-1
D) 731 JK-1

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Assessment 8
The constant pressure molar heat capacity, Cp,m ​, of methane
gas, CH4​, is 35.31 J K−1 mol−1 at temperatures close to 298 K.
Calculate the enthalpy change when 1.6 kg of methane gas is
heated from a temperature of 280 K to 320 K.

A) 103 kJ
B) 119 kJ
C) 132 kJ
D) 141 kJ

UST - DEPARTMENT OF CHEMICAL ENGINEERING 61

Assessment 9
The constant pressure molar heat capacity of argon, Cp,m​, is
20.79 J K−1 mol−1 at 298 K. What will be the value of the constant
A) 12.48 -1
J Kheat
volume molar capacity of argon, CV,m​, at this temperature?
mol-1
B) 16.53 J K-1
mol-1
C) 21.79 J K-1
mol-1
D) 29.10 J K-1
mol-1

UST - DEPARTMENT OF CHEMICAL ENGINEERING 62

Assessment 10
The constant pressure molar heat capacity, Cp,m​, of nitrogen
gas, N2​, is 29.125 J K−1 mol−1 at 298 K. Calculate the change in the
internal energy when 20 mol of nitrogen gas at 298 K is heated so
that its temperature increases by 15.0∘C. You may assume
A) 2.05
constant
kJ heat capacity over the temperature range.
B) 4.17
kJ
C) 6.24
kJ
D) 8.93
kJ

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 MODULE 2
CHE 216
Lecture 6:
1st
Law of
Thermodynamics
Part 2: Application of the First Law to Gases
D EPA R T MEN T OF C H EMIC A L EN GIN EER ING
U N IVER SIT Y O F SA N TO TO M A S
M A N IL A , PH IL IPPIN ES

UST - DEPARTMENT OF CHEMICAL

64
ENGINEERING
 Applications/Processes of
Thermodynamics
1. Constant Pressure – Isobaric
2. Constant Volume – Isochoric
CLOSED SYSTEM
3. Constant Temperature – Isothermal
(n is constant)
4. Adiabatic – no heat transfer

ADIABATIC ISOCHORIC ISOTHERMAL

(q = 0) (w = 0) (U = 0)
q
U w U q U
w
UST - DEPARTMENT OF CHEMICAL ENGINEERING 65
 Applications/Processes of
Thermodynamics
The First Law works differently for a process in which the volume stays
constant than for a process in which the pressure stays constant
Isochoric Process
The volume of the system remains constant (  V = 0). On a pV diagram,
this type of process would be represented by a vertical line. Therefore,
there is no area under the curve.

Since there is no change in volume, w = 0. So the internal energy of the

system depends only on heat transfer:  U = qV

Isobaric Process
The system's pressure is fixed ( p = 0). It is represented by a horizontal
line on a pV diagram.

Both w and q will still exist for this process:  U = q + w

UST - DEPARTMENT OF CHEMICAL ENGINEERING 66

 Applications/Processes of
Thermodynamics
Adiabatic Process
There is no transfer of heat to or from the system,  q = 0, though
other characteristics such as the pressure, volume, and temperature of
the system may vary. The curve of an adiabatic process on a pV
diagram depends on the changes in the system.
 U = wad
Isothermal Process
The system's temperature is fixed (  T = 0). It is represented by a pV
diagram and energy stays constant (  U = 0)

q = -w

Cyclic Process
Certain processes have the same initial and final states (e.g., engines).
This is represented by a closed path and  U = 0

q = -w
UST - DEPARTMENT OF CHEMICAL ENGINEERING 67
 1. Constant Volume - Isochoric
p

p2 P2, V,
P1, V,
T2 T1 T2
p1
T1 𝑈𝑓 𝑇𝑓
𝑑𝑈 = 𝑞𝑣 = 𝑛 𝐶𝑣 𝑑𝑇
V 𝑈𝑖 𝑇𝑖

V
∆𝑈 = 𝑞𝑣 = 𝑛 𝐶𝑣 𝑑𝑇 𝑤=0

UST - DEPARTMENT OF CHEMICAL ENGINEERING 68

 2. Constant Pressure- Isobaric
p

P, V2, T2
p P, V1, T1
T2

T1
V ∆𝑈 = 𝑛𝐶𝑣 ∆𝑇
V1 V2

UST - DEPARTMENT OF CHEMICAL ENGINEERING 69

Isobaric vs. Ischoric Processes

𝑞 = 𝑞𝑣 = 𝑛𝐶𝑣 ∆𝑇 𝑞 = 𝑞𝑝 = 𝑛𝐶𝑝 ∆𝑇
𝑤=0 𝑤 = −𝑝∆𝑉
∆𝑈 = 𝑞𝑣 = 𝑛𝐶𝑣 ∆𝑇 ∆𝑈 = 𝑛𝐶𝑣 ∆𝑇
UST - DEPARTMENT OF CHEMICAL ENGINEERING 70
More on Enthalpy
𝑑𝑈 = 𝜎𝑞 + 𝜎𝑤 𝑑𝐻 = 𝑑𝑞𝑝 = 𝑛𝐶𝑝 𝑑𝑇

𝑑𝑈 = 𝜎𝑞 − 𝑝𝑑𝑉 1 ∂H
𝐶𝑝 =
𝑛 ∂T 𝑃
𝑑𝑈 = 𝑑𝑞𝑝 − 𝑝𝑑𝑉

𝑑𝑈 = 𝑑𝐻 − 𝑝𝑑𝑉 𝑑𝑈 = 𝑑𝑞𝑣 = 𝑛𝐶𝑣 𝑑𝑇

𝑑𝐻 = 𝑑𝑈 + 𝑝𝑑𝑉 1 ∂U
𝐶𝑣 =
𝑛 ∂T 𝑉

UST - DEPARTMENT OF CHEMICAL ENGINEERING 71

Changes in Enthalpy (H)

Heat flow INTO Heat flow OUT

+q
SYSTEM -q
Enthalpy
H >0 (H) H <0
endothermic exothermic

UST - DEPARTMENT OF CHEMICAL ENGINEERING 72

More on Heat Capacities
Cp and Cv values for Monatomic Ideal Gases
𝑈 = 𝐾𝐸 + 𝑃𝐸
3 3
𝑈 = 𝐾𝐸 = 𝑛𝑅𝑇 𝐶𝑣 = 𝑅
2 2
3
∆𝑈 = 𝑛𝑅𝑇 = 𝑛𝐶𝑣 ∆𝑇
2
5
3 𝐶𝑝 = 𝑅
𝑛𝐶𝑣 ∆𝑇 = 𝑛𝑅∆𝑇 2
2

UST - DEPARTMENT OF CHEMICAL ENGINEERING 73

More on Heat Capacities
Cp and Cv values for diatomic Ideal Gases

5 7
𝐶𝑣 = 𝑅 𝐶𝑝 = 𝑅
2 2

UST - DEPARTMENT OF CHEMICAL ENGINEERING 74

3. Constant Temperature-
Isothermal

𝑉2
𝑤𝑟𝑒𝑣 = −𝑛𝑅𝑇 ln 𝑤𝑖𝑟𝑟𝑒𝑣 = −𝑝𝑒𝑥𝑡 ∆𝑉
𝑉1
𝑉2 𝑤𝑖𝑟𝑟𝑒𝑣 = 𝑝𝑒𝑥𝑡 ∆𝑉
𝑞𝑟𝑒𝑣 = 𝑛𝑅𝑇 ln
𝑉1
UST - DEPARTMENT OF CHEMICAL ENGINEERING 75
Problem
A 4.00 L sample of H2 gas at 1.50 atm and 25oC is allowed to
isothermally expand to a final pressure of 1.00 atm.
Calculate the q, w, U and H if the gas expands (a)
reversible and (b) irreversible

UST - DEPARTMENT OF CHEMICAL ENGINEERING 76

 4. Adiabatic
Isolated system  no heat flow
p
T1 > T 2
p1

T1
p2 P2, V2, T2
T2 P1, V1, T1
V
V1 V2
UST - DEPARTMENT OF CHEMICAL ENGINEERING 77
 4. Adiabatic
p
p1

T1 P2, V2, T2
P1, V1, T1
p2
T2

V1 V2
UST - DEPARTMENT OF CHEMICAL ENGINEERING 78
 Adiabatic - Reversible
(𝛾−1)
p 𝑇2 𝑉1
=
p1 𝑇1 𝑉2

𝛾−1
( )
T1 𝑇2 𝑃2 𝛾
=
p2 𝑇1 𝑃1
T2
𝛾 𝛾
𝑃2 𝑉2 = 𝑃1 𝑉1
V1 V2
UST - DEPARTMENT OF CHEMICAL ENGINEERING 79
Adiabatic - Reversible
𝑑𝑈 = 𝜎𝑞 + 𝜎w

𝑑𝑈 = 0 + 𝜎w

𝑑𝑈 = 𝑛𝐶𝑣 𝑑𝑇
𝑓𝑖𝑛𝑎𝑙 𝑇2
𝑑𝑈 = 𝑛𝐶𝑣 𝑑𝑇
𝑖𝑛𝑖𝑡𝑖𝑎𝑙 𝑇1

∆𝑈 = 𝑤 = 𝑛𝐶𝑣 ∆ 𝑇

UST - DEPARTMENT OF CHEMICAL ENGINEERING 80

 Adiabatic - Irreversible
p
p1 𝑃2 𝐶𝑣
𝑇2 +
𝑃1 𝑅
=
𝑇1 𝐶𝑣
+1
T1 𝑅
p2
T2

V1 V2

UST - DEPARTMENT OF CHEMICAL ENGINEERING 81

Problem
A 4.00 L sample of N2 gas at 15.00 atm and 25oC is
allowed to expand adiabatically to a final pressure
of 1.00 atm. Determine the q, w, H and U if the
gas expands in a (a) reversible and (b) irreversible
manner.

UST - DEPARTMENT OF CHEMICAL ENGINEERING 82

 Cyclic Process
P
2 mols of an ideal,
diatomic gas undergoes A B
P= 4 atm
a cyclic, reversible
process shown in the T = 200 K
diagram. Determine the
q, w, U and H for
P= 1 atm
each step of the C
process and for the
total cycle
V

83
 Cyclic Process
Suppose 0.100 mol of a P
perfect gas having Cv,m B C
P= 3 atm
1.50 R independent of
temperature undergoes
the reversible cyclic
process shown in the A D
right. Calculate the q, w, P= 1 atm
U and H for each step
V
of the process and for the 3 3
1000 cm 2000 cm
total cycle

UST - DEPARTMENT OF CHEMICAL ENGINEERING 84