Thermal & Statistical Physics

PHYS 404
First law of thermodynamics, energy, heat
capacity & enthalpy.
Lecture 2

1
Lecture 2 – 1st law of thermodynamics, energy, heat
capacities & enthalpy. (2 weeks)
1. Introduction
2. Heat & Work
3. The 1st Law of Thermodynamics
4. Thermodynamic Processes
5. Compression Work
6. Heat Capacity
7. Latent Heat
8. Enthalpy

2
 Learning Objectives
1. To identify by providing examples the difference between heat and
work.
2. To describe how heat is transferred by different heat mechanisms.
3. To explain the 1st law of thermodynamics.
4. To identify the algebraic sign of work done W and heat transfer Q.
5. To recognize important kinds of thermodynamic processes.
6. To analyze isothermal & adiabatic compression processes for an
ideal gas.
7. To calculate the work done for different thermodynamic processes.
8. To solve different problems on different thermodynamic processes.
3
 Learning Objectives
9. To demonstrate how heat transfer Q is related to substance’s
specific heat c & mass m for a temperature change ΔT.
10. To demonstrate how heat transfer Q is related to substance’s molar
heat capacity C & no. of moles n for a temperature change ΔT.
11. To compare b/w heat capacities at constant volume and pressure.
12. To demonstrate how the heat capacities of a gas reveal whether its
molecules are rotating or vibrating.
13. To show how the heat transfer Q, the heat of transformation L, and
the amount of mass m transformed are related.
14. To explain how enthalpy is considered more useful quantity than
internal energy of a given thermodynamic system.
4
Introduction

• Much of thermodynamics deals with three closely related concepts:

temperature, energy, and heat.
• Energy is the most fundamental dynamical concept in all of physics,
which couldn’t be explained in terms of more fundamental thing.

• There are 2 main mechanisms by which energy can be put into or

taken out of a system.

• Heat: is any spontaneous flow of energy from one object to another,

caused by a difference in temperature between the objects.

• Work: is any other transfer of energy into or out of a system.

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6
Heat & Work in One Example
Example 1:

• What is cause of change of temperature in the following cases:

1. Pushing a piston of a given container.
2. Putting a warm radiator into a cold room.
3. Stirring a cup of coffee.
4. Putting a cold ice into hot water.
5. Rubbing both hands together to warm them up.
6. The sunshine exchanged between sun & earth.
7. Entering a cup of tea to warm it up in the microwave.

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1- A good example of a thermodynamic system is gas confined by a
piston in a cylinder. Pushing a piston (work), so pressure increase and
the amount of collisions increases this means that the amount of
EFFECTIVE collisions also increase, and also the rate at which the
molecules move is also increased. This is the cause of temperature, an
increase in speed of vibration. This is why temperature increases.
2- Convection currents are created when the air above your
radiator heats and then cools and is then heated again. This
process happens continuously whilst you have your heating on and the
current moves the heat around the room making it nice and warm and
toasty.
3- Stirring will help cool a hot drink because it speeds up the process
of convection by bringing the hottest liquid at the bottom to the
top, where it can be cooled by the air.
4- Water can exist as a solid (ice), liquid (water) or gas (vapor). Adding
heat can cause ice (a solid) to melt to form water (a liquid).
Removing heat causes water (a liquid) to freeze to form ice (a solid). 8
5- When you rub your hands together, the action of scraping the surface
of your skin back and forth against each other causes the molecules in
your skin to move a little faster. The faster that molecules move, the
higher the temperature. So the friction of rubbing your hands together
makes them feel warmer.
6- Radiation is the transfer of heat energy through space by
electromagnetic radiation. Most of the electromagnetic radiation that
comes to the earth from the sun is invisible. Only a small portion comes
as visible light.
7- In a microwave oven the water will super-heat and may suddenly
boil. Water molecules vibrate when they absorb microwave energy, and
the friction between the molecules results in heating (increase
temperature)

9
 Example 2:

• A battery is connected in series to a resistor, which is immersed in water

(to prepare a nice hot cup of tea). Would you classify the flow of energy
from the battery to the resistor as "heat" or "work"? What about the flow
of energy from the resistor to the water? Explain both answers.

The flow of energy from the battery to the resistor is work, because the
energy transferred by the electrons moving through the resistor is
driven by the voltage difference, it doesn’t occur spontaneously due to a
temperature difference. The flow of energy from the resistors to the
water, though, is heat: a spontaneous flow of energy from one object
(resistors) to another (water) caused by the difference in temperature
between the objects
10
Joule’s Experiment
• It was James Joule & others who demonstrated that the same
temperature increase could be accomplished by doing mechanical work
instead of adding heat.

We’ll explore the relationship

between heat and mechanical
energy

The same temperature change can

also be caused by putting the water The paddle wheel adds energy to the water
in contact with some hotter body; by doing work on it, and Joule found
hence this interaction must also that the temperature rise is directly
involve an energy exchange. proportional to the amount of work done. 11
The 1st Law of Thermodynamics
1st Law of Thermodynamics:
“The total internal energy that enters a thermodynamic system equals
the heat added and the work done”
Heat added
Work done
to system
on system

• It is a generalization statement of the

law of conservation of energy.

• Both Q and W depend on the path

chosen between states, but ∆U is
independent of the path.

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The 1st Law of Thermodynamics

• If the changes are infinitesimal, we can write the 1st law as

dU = dQ + dW

• SI unit of energy is joule, defined as 1 kg·m2 /s2.

• Traditionally, however, heat energy has been measured in calories.

• 1 calorie (abbreviated cal) is the amount of heat needed to raise the

temperature of 1 gram of water by 1°C (precisely) from 14.5-15.5°C.

• 1 cal = 4.186 J.

13
The 1st Law of Thermodynamics

• Heat signs!

• Q is –ve if heat
leaves out a
system.

• Q is +ve if heat
flows into a
system.

14
The 1st Law of Thermodynamics

• Careful of work signs! (According to chemists (IUPAC) & some

physicists convention)

• When work is done by a system, the system undergoes expansion,

and by convention, W is –ve.

• When work is done on a system, the system undergoes

compression, and by convention, W is +ve.

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Work Done During Volume Changes/Quasi-Static
• Here, it is assumed that the gas is
compressed or expands in internal
equilibrium, i.e., its pressure is
uniform from place to place.

• Thus, the piston's motion must be

reasonably slow, so that the gas has
time to continually equilibrate to
the changing conditions.

• The technical term for a volume change that is slow in this sense is
quasi-static.

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Work Done During Volume Changes
• Therefore, we can consider the infinitesimal
work done by the system during the small
expansion dx, i.e.

In a finite change of volume from V1 to V2:

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• In this case the work is positive.

18
Work Depends on the Path Chosen
• Consider three different paths on a pV-diagram for getting from state 1 to
state 2.

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Work Depends on the Path Chosen

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Internal energy is a state function (path independent)

• The internal energy of a cup of

coffee depends on just its
thermodynamic state i.e., how
much water and ground coffee
it contains, and what its
temperature.

• It does not depend on the history

(path) of how the coffee was
prepared i.e., the thermodynamic
path that led to its current state.

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Thermodynamic Processes dU = dQ + dW and W=P dV

• There are 4 specific kinds of thermodynamic processes that occur often

in practical situations:
• Adiabatic: No heat is transferred into or out of the system, so
Q = 0. Also, ∆ U = W
• Isochoric (isovolumic): The volume remains constant i.e.
W = 0 (dV = 0) so ∆ U = Q
• Isobaric: The pressure remains constant, so
W = P(V2 – V1)
• Isothermal: The temperature remains constant, i.e.
dT = 0, so dU = 0 and thus Q = - W
22
Thermodynamic Processes

• Remarks:

• In a cyclical process with a gas, there is no net change in the

internal energy ΔU, and thus Q = - W.

• For free expansion case, which is an irreversible process in

which a gas expands into an insulated evacuated chamber,

Q = W = 0, Thus ΔU = 0.

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PV-diagram & Isotherms
Boyle's law, also referred to as the Boyle–Mariotte law, or Mariotte's
law (especially in France), is an experimental gas law that describes the
relationship between pressure and volume of a confined gas. Boyle's
law has been stated as:
The absolute pressure exerted by a given mass of an ideal gas is
inversely proportional to the volume it occupies if the temperature and
amount of gas remain unchanged within a closed system.

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Phases of matter
• Atmospheric pressure on
earth is higher than the
triple-point pressure of
water.
• Depending on the
temperature, water can
exist as a vapor (in the
atmosphere), as a liquid
(in the ocean), or as a
solid (like the iceberg
shown here).

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Phases of matter
• For an ideal gas we ignore the interactions between molecules.
• But those interactions are what makes matter condense into the
liquid and solid phases under some conditions.
• Each phase is stable in only certain ranges of temperature and
pressure.
• A transition from one phase to another ordinarily requires phase
equilibrium between the two phases, and for a given pressure this
occurs at only one specific temperature.
• We can represent these conditions on a graph with axes p and T,
called a phase diagram. (See next slide.)
• Each point on the diagram represents a pair of values of p and T.

26
A typical pT phase diagram

27
pVT-surface for a substance that expands on melting
• A pVT-surface graphically represents the equation of
state.
• Projections onto the pT- and pV-planes are shown.

28
pVT-surface for an ideal gas
• The pVT-surface for an ideal gas is much simpler than
the pVT-surface for a real substance, as seen in the
previous slide.

29
PV-diagram & Constant line

30
Thermodynamic Processes on PV-diagram

31
Adiabatic Processes for an Ideal Gas
• In an adiabatic process, no
heat is transferred in or out of
the gas, so Q = 0.
• Shown is a pV-diagram for an
adiabatic expansion.
• As the gas expands, it does
positive work W on its
environment, so its internal
energy decreases, and its
temperature drops.
• Note that an adiabatic curve at any point is always
steeper than an isotherm at that point.
32
Adiabatic Process/ Real Life Examples
• Put your hand a few centimeters in
front of your mouth, open your mouth
wide, and exhale.
• Your breath will feel warm on your
hand, because the exhaled gases
emerge at roughly the temperature of
your body’s interior.
• Now purse your lips as though you
were going to whistle, and again blow
on your hand.
• The exhaled gases will feel much cooler.
• In this case the gases undergo a rapid, essentially adiabatic
expansion as they emerge from between your lips, so the
temperature of the exhaled gases decreases.
33
Adiabatic Process/ Real Life Examples
Adiabatic processes are used in the Otto cycle (when the piston does
work on the gasoline)

The video below demonstrates an adiabatic compression: the

temperature inside the chamber is increased enough to ignite the
cotton.

34
Isobaric Process/ Real Life Examples

• Most cooking involves

isobaric processes.

• That’s because the air

pressure above a saucepan
or frying pan, or inside a
microwave oven, remains
essentially constant while
the food is being heated.

35
 Example 3:

• An ideal gas is made to undergo a cyclic process. For each of the steps A,
B, and C, determine whether each of the following is positive, negative,
or zero:
a) The work done on the gas.
b) The change in the energy content
of the gas.
c) The heat added to the gas.
d) The sign of each of these three
quantities for the whole cycle.

36
 Example 3:
Work done on the gas (done by the surrounding)

• For system containing N

molecules, each with f
degrees of freedom, then
total thermal energy is

37
 Example 3:
Heat added to the gas (reference)
So work done by the gas=-(Work done on the gas)

38
 Example 3:

d) The sign of each of these three quantities for the whole cycle.
The results are listed in this table:
The gas is the reference
Apparently, the net result of the cycle is
gas absorb energy as work (W>0) and
emit energy as heat (Q<0)

WC is higher than WA in absolute value as for path C, Pf is higher than Pi.

For the whole cycle the energy must be unchanged, since initial and final
P and V are unchanged.
As concequence, Q<0. 39
 Example 4:
• The process abc shown in the PV-diagram of 0.0175 mole of an ideal gas.
a) What was the lowest temperature the
gas reached in this process? Where
did it occur?
b) How much work was done by or on
the gas from a to b? From b to c?
c) If 215 J of heat was put into the gas
during abc, how many of those
joules went into internal energy?

40
41
 Example 5:
• Two moles of an ideal gas are heated at constant pressure
from 27 oC to 107 oC.
a) Draw a PV-diagram for this process?
b) Calculate the work done by the gas.

It is a isobaric process

As the work is done by the gas, it’s negative so W = -1330 J

42
Compression of an Ideal Gas

• There are 2 idealized ways of compression an ideal gas;

1. Isothermal compression (slow compression): the gas is

compressed very slowly in such away that its temperature
doesn't rise at all.

2. Adiabatic compression (fast compression): the gas is

compressed very fast in such away no heat escapes from the gas
during the process.

43
Compression of an Ideal Gas

1. Isothermal compression:
- This process is considered a
quasi-static process.
- The work done by the gas is
minus the area under the graph.

Work is negative 44
 Compression of an Ideal Gas
• To calculate the heat entering or leaving a system undergoing an
isothermal process, we use 1st law of thermodynamics:

• Conclusions:

1. Heat input is just minus (opposite) the work done @ isothermal process.

2. For isothermal compression, Q is -ve and heat leaves the gas.

3. For isothermal expansion (see example below), Q will be +ve, and heat
enters the gas.
45
heat is positive, its enters the gas 46
Compression of an Ideal Gas
2. Adiabatic compression
(fast compression):

Here, Q = 0 & ∆ U = -Wdone by gas

47
Compression of an Ideal Gas

Where γ: Adiabatic exponent = (f+2)/f

48
 Example 6:

• Two moles of an ideal gas are compressed in a cylinder at a constant

temperature of 85 oC until the original pressure has tripled. (a) Sketch a
PV-diagram for this process. (b) Calculate the amount of work done.

(b)

49
 Example 7:
• Five moles of an ideal monatomic gas with an initial temperature of 127
oC expand and, in the process, absorb 1200 J of heat and do 2100 J of

work. What is the final temperature of the gas?

According to first law of thermodynamics, ∆U= Q-W

Where +Q is heat added to system. W is work done by the gas.
∆U is change in internal energy= 1200-2100=-900J.
Now, ∆U=(f/2)NK ∆T=(f/2)n.NAK ∆T=(f/2)n.R ∆T
Where n(#.of moles of gas),R(universal gas constant),∆T(change in
temperature) and f degrees of freedom=3 for monatomic gas
U  900
T    14 .44
3 7.5 * 8.31
nR
2
Tf  Ti  14 .44  127  14 .44  112 .56 C
50
 Example 8:
• In the course of pumping up a bicycle tire, a liter of air at atmospheric
pressure is compressed adiabatically to a pressure of 7 atm. (Air is
mostly diatomic nitrogen and oxygen.)
a) What is the final volume of this air after compression?
b) How much work is done in compressing the air?
c) If the temperature of the air is initially 300 K, what is the temperature
after compression?

51
a) What is the final volume of this air after compression?

=(f+2)/2 f=5 for

diatomic N
and O
.

b) How much work is done in compressing the air?

(f/2)n.R ∆T=
5
U  (7  1.013  10 5  0.25  10 3  1.013  10 5  10 3 )
2
5
U   1.013  10 5  10 3 (7  0.25  1)  189 .9 J 52
2
c) If the temperature of the air is initially 300 K, what is the temperature after
compression?

0 .4
 1  300 0.5 
Tf     522 .33 K
 1 
 4 

53
 Example 9:
• Two moles of carbon monoxide (CO) start at a pressure of 1.2 atm and a
volume of 30 liters. The gas is then compressed adiabatically to 1/3 of
this volume. Assume that the gas may be treated as ideal. What is the
change in the internal energy of the gas? Does the internal energy
increase or decrease? Does the temperature of the gas increase or
decrease during this process? Explain.

54
55
Heat Capacity

Heat Capacity: It is the amount of heat needed to raise the temperature

of an object by a given amount.

• In other words: It is a proportionality constant that relates the amount

heat Q absorbed/lost by an object and the resulting temperature
change ΔT of the object.

56
Specific Heat Capacity
• More fundamental quantities than heat capacity are used to describe
the properties of a substance in more detailed manner which are;
specific heat capacity & molar heat capacity.

Specific Heat Capacity: It is the quantity of heat Q required to increase

the temperature of a mass m of a certain material by ΔT.

57
 Specific Heat Capacity
• For an infinitesimal temperature change dT and corresponding quantity
of heat dQ are given by;
Water has a high specific heat capacity (4.18J/g/K) compared to
other substances, thus more heat is required to raise its
temperature. This can be explained by water's strong hydrogen
bonds.
Water exhibits strong hydrogen bonds between its molecules (the
• Specific heatintermolecular
strongest capacity is basically theWhen
force). heat capacity
heat isperabsorbed,
unit mass; the
energy goes to these intermolecular forces (IMFs). The stronger
the IMFs are, the more heat they can absorb, and as water
exhibits the strongest IMF, it has a higher heat capacity than other
• The specific heat capacity has different values for different materials.
substances.

• The specific heat capacity of water is approximately 4190 J/kg∙K, which

is considered the highest amongst materials, why?

58
 Specific Heat Capacity/Real Life examples

• Q) Explain why it takes

While a several
typical minutes
empty to boilwould
pot
water on a stove, evenweigh
hardly thoughathe pot few
very or kettle
100s of
reaches a high grams,
temperature
a panvery
full quickly?
of water will weigh
several times over and therefore the
amount of heat required and hence
the time to get hot would be
proportionately high as well.
Secondly, the specific heat of metals
are only a small fraction of that of
water so metals will heat up much
faster. Lastly, a pot is metallic and so
conducts heat very well and got very
hot very quickly but water heats up
by convection and so heats relatively
gradually. 59
 Determination of Specific Heat Capacity Experimentally

• Here, measured quantity of energy is supplied by an electric current in a

heater wire wound around the specimen.

• The temperature change is measured with a resistance thermometer or

thermocouple embedded in the specimen.

• Great care is needed to

avoid or compensate for
unwanted heat transfer
between the sample and
its surroundings.

60
 Molar Heat Capacity

Molar Heat Capacity: It is the quantity of heat Q required to increase

the temperature of n moles of a certain material by ΔT.

• Where C = c.M (M is the molar mass of the substance )

61
 Molar Heat Capacity

• Molar heat capacity is basically the heat capacity per mole of the system.

• For an infinitesimal temperature change dT and corresponding quantity

of heat dQ are given by;

• The molar heat capacity has different values for different materials.

• The molar heat capacity of water is approximately 75.4 J/mol∙K.

62
Specific Heats & Molar Heat Capacities

63
Example 10:

Q A  m A c A TA
Q B  m B c B TB
But m A  m B and Q A  Q B  Q
Q A c A TA c TB 4
  1 A   1
QB c B TB c B TA 3
 cA  cB

64
 Example 11:
• A person pours 330 g of water at 45°C into an 855-g aluminum container
with an initial temperature of 10°C. The specific heat of aluminum is 900
J/kg.K and that of water is 4190 J/kg.K. What is the final temperature of
the system, assuming no heat is exchanged with the surroundings?

65
 Example 12:
• Estimate how long it should take to bring a cup of water of 200 g at a
temperature of 20 oC to boiling temperature in a typical 600-watt
microwave oven, assuming that all the energy ends up in the water.

66
 Example 13:
• You are designing an electronic circuit element made of 23 mg of silicon.
The electric current through it adds energy at the rate of 7.4 mW. If your
design doesn’t allow any heat transfer out of the element, at what rate
does its temperature increase? The specific heat of silicon is 705 J/kg.K.

67
 Conditions Affecting Heat Capacity
• The heat capacity value depends on certain circumstances.

• To verify this, we plug the 1st law of thermodynamics in the heat

capacity eqn, thus we get:

• In practice, there are two types of circumstances that are most likely to
occur:

1. Heat capacity taken at constant volume, Cv.

2. Heat capacity taken at constant pressure, Cp.

68
Heat Capacity at Constant Volume Cv

1. Heat capacity at
constant volume, Cv:

- Here, the system's volume

isn't changing, which means
that W = 0.

- If we have n number of moles of an ideal gas, then CV is denoted as

molar heat capacity at constant volume.

69
 Heat Capacity at Constant Pressure Cp
2. Heat capacity at constant
pressure, Cp:
- Here, the system's pressure isn't
If you keep pressure
changing, which means W ≠ 0. constant and add
heat, you need to
- This represents most of our change volume. Some
everyday life examples. of the heat is used to
increase temperature
and some of the heat
is used to do work to
change volume.
- For solids and liquids, is usually small and can often be neglected.

- For gases, however, the 2nd term is quite significant (The 1st term also is
not quite the same as Cv ).
70
 Prediction of Heat Capacity Theoretically
• Suppose that our system stores thermal energy only in quadratic
"degrees of freedom" as described by equitation theorem, then we get:

• Remarks:

- This result gives us a direct method of measuring the number of degrees

of freedom in an object.

- It doesn't matter whether V or P is held fixed in the derivative.

71
 Prediction of Heat Capacity for an Ideal Gas Theoretically
• For an ideal monatomic gas (E.g., He): f =3, then Cv = 3/2 Nk = 3/2 nR.
• Thus, Cv per mole is:

• For an ideal diatomic gas (E.g., CO): f =5, then Cv = 5/2 Nk = 5/2 nR.
• Thus, Cv per mole is:

72
Compare b/w Theoretical & Experimental Heat Capacities
• Experimental values of CV for different types of gas molecules

73
Compare b/w Theoretical & Experimental Heat Capacities
• Experimental values of CV for hydrogen gas (H2).

• Note that the temperature scale is logarithmic.

• At atmospheric pressure,
hydrogen liquefies at 20 K
The vibrational degrees of freedom are frozen
and begins to dissociate at
aboutout
2000at
K. low temperature for a number of diatomic
gases.
• For most of diatomic
gases, however, vibrational
motion doesn’t contribute
appreciably to heat
Figure is a graph of the temperature dependence of CV
capacity, why? for hydrogen gas (H2), showing the temperatures
at which the rotational and vibrational energies begin to
contribute.
74
Relating Cp and CV for an Ideal Gas
• Thus, the 2nd term for the heat
capacity at constant pressure
gives us:

• Therefore, the heat capacity

at constant pressure becomes:

• For one mole of an ideal gas:

75
Relationship between Cv and Cp for ideal gas
From first low of thermodynamics:

Q  E  W
nC v  T  nC p  T  P  V
nC v  T  nC p  T  nR  T
C p  Cv  R

f  f 2
Cp  R  R   R
2  2 

76
Relating Cp and CV for an Ideal Gas
• Dividing both sides by CV , this gives us the ratio of heat capacities as:

• For monatomic ideal gases, γ = 1.67

• For diatomic ideal gases, γ = 1.40

• For polyatomic ideal gases, γ = 1.33

77
 Example 14:

• Assume that helium behaves as an ideal monatomic gas. If 2 moles of

helium undergo a temperature increase of 100 K at constant pressure,
how much energy has been transferred to the helium as heat?

78
 Example 15:

• 5 and then—4,3,2,1—with same ∆U.

79
 Example 16:
• A cylinder with a fixed volume contains hydrogen (H2) gas at 25 K. You then
add heat to the gas at a constant rate until its temperature reaches 500 K.
a) Does the temperature of the gas increase at a constant rate? Why or why
not?
b) If not, does the temperature increase most rapidly near the
beginning or during process?

a) No as the variation of Cv is not

monotonic. Q=nCvT
b) During process
80
 Example 17:
• One mole of ideal gas is slowly compressed to one-third of its original
volume. In this compression, the work done on the gas has magnitude
600 J. For the gas, Cp =7R/2 .
a) If the process is isothermal, what is the heat flow Q for the gas? Does
heat flow into or out of the gas?
b) If the process is isobaric, what is the change in internal energy of the
gas? Does the internal energy increase or decrease?
-w

a)  U=Q+W= n Cp T=0Q =-W= - 600 J.

b) ∆U = -1500 J.
81
 Example 18:
• Three moles of an ideal gas are taken around the cycle
acb as shown in the Figure. For this gas, Cp = 29.1 J/mol.K. Process ac
is at constant pressure, process ba is at constant volume,
and process cb is adiabatic. The temperatures of the gas in states a, c,
and b are Ta = 300 K, Tc = 492 K, Tb = 600 K. Calculate the total work
W for the cycle.

82
83
 Latent Heat
Latent heat, energy absorbed or released by a substance during a
change in its physical state (phase) that occurs without changing
its temperature.
• We knew how heat is involved in
temperature changes.

• In some situations, heat can be put

into a system without increasing its
temperature at all!

• This normally happens at a phase

transformation, such as melting
ice or boiling water.

• Then
84
 Latent Heat
Latent Heat of transformation (L): It is the amount of heat required
during phase transformation to melt or boil the substance completely
divided by the mass of the substance.

• Numbers for comparison: Raising the temperature of water from

0 oC to 100 oC requires 100 cal/g.

• The latent heat for melting ice is 333 J/g, or 80 cal/g.

• The latent heat for boiling water is 2260 J/g, or 540 cal/g.
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 Latent Heat of Fusion
• Latent heat of transformation is of 2 types:

1. Latent heat of fusion: Heat required for changing solid phase to

liquid phase and vise-versa.
• Here both phases coexists at same
temperature (freezing/melting Temp.)
a fact known as phase equilibrium.

• Example: The metal gallium. Its

melting temperature is 29.8 oC and its
heat of fusion is 8.04 × 104 J/kg.

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 Latent Heat of Vaporization
2. Latent heat of vaporization: Heat required for changing liquid phase
to gaseous phase and vise-versa.
• Here both phases coexists at same temperature (Condensing/Boiling
Temperature)

• Real Life Examples:

- A pot of water may reach boiling temperature in a few minutes, but it

takes a much longer time to completely evaporate all the water away.

- The water may be warm and it may be a hot day, but these children
will feel cold when they first step out of the swimming pool in
phenomenon known as evaporative cooling.
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Latent Heat/Example
Q) Why the line for the solid phase (ice) has a steeper slope than does
the line for the liquid phase (water)?

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 Example 19:
• Your 200-g cup of tea is boiling-hot. About how much ice should you
add to bring it down to a comfortable sipping temperature of 65°C?
(Assume that the ice is initially at -15°C. The specific heat capacity of
ice is 0.5 cal/g·oC, latent heat of fusion for ice 80 cal/g & specific heat
capacity of water 1 cal/g.oC).

Q  m c T

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 Latent Heat/Other Types
• Latent heat of sublimation (Ls): It is an amount of heat needed to
change a substance directly from the solid to the gaseous phase
(without any intermediate state at a constant temperature).
• Examples:
1. Liquid carbon dioxide can’t exist at a pressure < 5 atm. Therefore, its
“dry ice” (solid carbon dioxide) sublimes at atmospheric pressure.
2. Principle of clouds seeding involves
modifying a cloud's structure to
increase the chance of precipitation.
https://letstalkscience.ca/educational-
resources/stem-in-context/what-cloud-
seeding
90
 Latent Heat/Other Types

• Chemical reactions such as combustion are analogous to phase

changes in that they involve definite quantities of heat.

• Complete combustion of 1 gram of gasoline produces about 46,000 J

or about 11,000 cal, so the heat of combustion Lc of gasoline is

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Heat of Fusion & Vaporization of Different Substances

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 Example 20:
• A hot copper pot of mass 2.0 kg (including its copper lid) is at a
temperature of 150 °C . You pour 0.10 kg of cool water at 25°C into the
pot, then quickly replace the lid so no steam can escape. (cW = 4190
J/kg.K and cCu = 390 J/kg.K). Find
1. the final temperature of the pot and its contents.
2. Determine the phase of the water (liquid, gas, or a mixture). Assume
that no heat is lost to the surroundings.

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But this is above the boiling
point of water, which
contradicts our assumption
that no water boils! So at
least some of the water
boils.

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 Example 21:
• In a particular camp stove, only 30% of the energy released in burning
gasoline goes to heating the water in a pot on the stove. How much
gasoline must we burn to heat 1.00 L (1.00 kg) of water from 20 °C to
100 °C and boil away 0.25 kg of it? (Lc of gasoline is 46000 J/g).

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Enthalpy

• The changes of phase of a pure substance were described (latent heat)

but no reference was made to the work accompanying these changes.

• Changes of phase are always associated with changes in volume, so

that work is always done on or by a system in a phase change.

• Many of these changes takes place most often at constant pressure

whether in the natural world or in the laboratory.

• Therefore, instead of always talking about the energy content of a

system, we can agree to always add in the work needed to make room
for it (under a constant pressure, usually 1 atm), e.g., sea & water in a
glass.

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 Enthalpy
• This work is PV, i.e., the pressure of the environment times the total
volume of the system. Adding PV onto the energy gives a quantity
called the enthalpy, denoted H:

97
Enthalpy

98
 Enthalpy Change & Work
• The general form of 1st law of thermodynamics states that the change in
internal energy equals the heat added to the system, plus the
compression-expansion work done on it, plus any other work (e.g.,
electrical) done on it i.e.

• Combining the last 2 eqn, we get:

• Implication: This eqn suggests that the change in enthalpy is caused

only by heat and other forms of work, NOT by compression-expansion
work during constant-pressure processes.

99
 Enthalpy & Specific Heat at Constant Pressure
• If no "other" types of work are being done, the change in enthalpy
would be the heat added to the system, thus at constant pressure Cp is:

• Cp is referred to as "enthalpy capacity".

• ∆H is useful in many dramatic processes such as phase transformations,

chemical reactions, ionization, dissolution in solvents,…etc.

• Example: Consider the chemical reaction

- For each mole of water produced, ∆H for this reaction is -286 kJ; this
quantity is referred to as the enthalpy of formation of water, because it's
being ''formed'' out of elemental constituents in their most stable states.
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Useful Tables

101
Useful Tables

102
 Example 22:

• Boiling one mole of water at 1 atm has ∆H of 40,660 J (from table).

1. How much heat is required to boil 1 g of water? What does this value
indicate?
2. How much do you think the energy required to push the atmosphere a
way for the vapor?

1. H=Q =40,660J for 1 mole

The heat required to boil 1 g of water is latent heat
Lv =Q/m=40660/18  2260 J/g
2. The volume of one mole of water, according to the ideal gas law is
RT/P, so the work needed to push the atmosphere away is:
103
 Example 23:
• Consider the combustion of one mole of H2 with 1/2 mole of O2 under
standard conditions with ∆H = -286 kJ.
1. How much comes from the work done by the collapsing atmosphere?
(Treat the volume of the liquid water as negligible.)
2. How much of the heat energy produced (lost by the reactants) comes
from a decrease in the energy of the system?

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1. W = - 3.7 kJ

2. ∆U = - 282 kJ

105
 Example 24 (thermochemistry):
• Consider the combustion of one mole of methane gas:

Where for one mole of gas, ∆HCH4 = -74.81 kJ, ∆HCO2 = -393.51 kJ,
∆HH2O(vapor) = -241.82 kJ.
1. What is ∆H for this reaction?
2. How much heat is given off (lost) during this reaction, assuming that no
"other“ forms of work are done ? Is this reaction endo- or exothermic?

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∆H = -802.34 kJ
107
(2)

Q = 802.34 kJ

108