Chapter 2
Chapter 2
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
5
6
Heat & Work in One Example
Example 1:
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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)
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Example 2:
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
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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.
12
The 1st Law of Thermodynamics
dU = dQ + dW
• 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
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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.
• The technical term for a volume change that is slow in this sense is
quasi-static.
16
Work Done During Volume Changes
• Therefore, we can consider the infinitesimal
work done by the system during the small
expansion dx, i.e.
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• In this case the work is positive.
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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
20
Internal energy is a state function (path independent)
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Thermodynamic Processes dU = dQ + dW and W=P dV
• Remarks:
Q = W = 0, Thus ΔU = 0.
23
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.
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A typical pT phase diagram
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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.
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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)
34
Isobaric Process/ Real Life Examples
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.
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Example 3:
Work done on the gas (done by the surrounding)
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Example 3:
Heat added to the gas (reference)
So work done by the gas=-(Work done on the gas)
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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)
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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
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Compression of an Ideal Gas
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.
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):
47
Compression of an Ideal Gas
(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
51
a) What is the final volume of this air after compression?
(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.
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55
Heat Capacity
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.
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.
58
Specific Heat Capacity/Real Life examples
60
Molar Heat Capacity
61
Molar Heat Capacity
• Molar heat capacity is basically the heat capacity per mole of the system.
• The molar heat capacity has different values for different materials.
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
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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.
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Conditions Affecting Heat Capacity
• The heat capacity value depends on certain circumstances.
• In practice, there are two types of circumstances that are most likely to
occur:
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Heat Capacity at Constant Volume Cv
1. Heat capacity at
constant volume, Cv:
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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 ).
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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:
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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
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Compare b/w Theoretical & Experimental Heat Capacities
• Experimental values of CV for hydrogen gas (H2).
• 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:
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
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Relating Cp and CV for an Ideal Gas
• Dividing both sides by CV , this gives us the ratio of heat capacities as:
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Example 14:
78
Example 15:
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?
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.
• 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.
• The latent heat for boiling water is 2260 J/g, or 540 cal/g.
85
Latent Heat of Fusion
• Latent heat of transformation is of 2 types:
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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)
- 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.
87
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)?
88
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
89
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
91
Heat of Fusion & Vaporization of Different Substances
92
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.
93
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.
94
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
96
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.
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:
- 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.
100
Useful Tables
101
Useful Tables
102
Example 22:
104
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?
106
∆H = -802.34 kJ
107
(2)
Q = 802.34 kJ
108