1.

THERMODYNAMICS PROCESSES
• Isochoric process means constant
volume, e.g., in a close constant-
volume container
Importance: pdV work is zero

• Isobaric process means constant

pressure, e.g., in atmospheric pressure
Importance: pdV work is 𝑝 𝑉! − 𝑉"

• Isothermal process means constant

temperature, i.e., isotherms in a pV
diagram
Adiabatic process
• means Q = 0

It may be
1. A thermally insulated system where heat cannot enter or leave, e.g. in a thermal flask
2. A quick process where heat has no time to go in or out, e.g., by conduction

• Adiabatic expansion,
𝑊 > 0 ⇒ ∆𝑈 < 0
usually leads to cooling

• Adiabatic compression,
𝑊 < 0 ⇒ ∆𝑈 > 0
usually leads to heating
Free Expansion
“Free” means at no cost
An isolated system (𝑄 = 0) expands into
vacuum, no work needed, 𝑊 = 0, then ∆𝑈 = 0,
internal energy does not change

Experimental results:

1. For dilute gas, no 2. For other gases,

temperature change temperature drops
conclusion
conclusion
For real gas with intermolecular attraction,
expansion → molecules farther apart →
For ideal gas, 𝑈 depends on T only, increase (less -ve) in PE
not on p or V, consistent with ∆𝑈 = 0 → KE decreases
kinetic theory T drops → T directly related to KE
Q19.10

An ideal gas is taken around the cycle

shown in this p-V diagram, from a to c to b
and back to a. Process c ® b is adiabatic.
For process c ® b,

A. Q > 0, W > 0, and DU = 0.

B. Q > 0, W > 0, and DU > 0.
C. Q = 0, W > 0, and DU < 0.
D. Q = 0, W < 0, and DU > 0.
E. Q < 0, W < 0, and DU = 0.
A19.10

An ideal gas is taken around the cycle shown

in this p-V diagram, from a to c to b and
back to a. Process c ® b is adiabatic.
For process c ® b,

A. Q > 0, W > 0, and DU = 0.

B. Q > 0, W > 0, and DU > 0.
C. Q = 0, W > 0, and DU < 0.
D. Q = 0, W < 0, and DU > 0.
E. Q < 0, W < 0, and DU = 0.
Q19.11

When an ideal gas is allowed to expand isothermally from volume V1 to a larger

volume V2, the gas does an amount of work equal to W12.
If the same ideal gas is allowed to expand adiabatically from volume V1 to a larger
volume V2, the gas does an amount of work that is

A. equal to W12.
B. less than W12.
C. greater than W12.
D. either A., B., or C., depending on the ratio of V2 to V1.
A19.11

When an ideal gas is allowed to expand isothermally from volume V1 to a larger

volume V2, the gas does an amount of work equal to W12.
If the same ideal gas is allowed to expand adiabatically from volume V1 to a larger
volume V2, the gas does an amount of work that is

A. equal to W12.
B. less than W12.
C. greater than W12.
D. either A., B., or C., depending on the ratio of V2 to V1.
Adiabatic Process for Ideal Gas Qualitatively:
For an ideal gas, 𝑈 depends on T only
adiabatic compression: 𝑊 < 0, ∆𝑈 > 0 ⇒ heating
adiabatic expansion: 𝑊 > 0, ∆𝑈 < 0 ⇒ cooling

Analytically:
For any process (whether adiabatic or not)
!
𝑑𝑈 = " 𝑛𝑅𝑑𝑇
For an adiabatic process
𝑛𝑅𝑇
𝑑𝑈 = −𝑑𝑊 = −𝑝𝑑𝑉 = − 𝑑𝑉
𝑉
𝑑𝑇 2 𝑑𝑉
⇒ + =0
𝑇 𝑓 𝑉

𝐶# − 𝐶$ 𝑅 2 𝑑𝑇 𝑑𝑉
𝛾−1= = = + 𝛾−1 =0
𝐶$ 𝑓 𝑓
2
𝑅 𝑇 𝑉
𝑑𝑇 and 𝑑𝑉 are of opposite signs, i.e., if 𝑑𝑉 > 0 (expansion), 𝑑𝑇 < 0 (cooling), etc.
 𝑑𝑇 𝑑𝑉
+ 𝛾−1 =0
𝑇 𝑉

Integrating, get
ln 𝑇 + 𝛾 − 1 ln 𝑉 = constant

ln 𝑇𝑉 #$" = constant

𝑇𝑉 #$" = constant

Eliminate T by using 𝑇 = 𝑝𝑉/𝑛𝑅

𝑝𝑉 #$"
𝑉 = constant
𝑛𝑅

𝑃𝑉 # = constant
Work done by the ideal gas in an adiabatic process

𝑓
𝑊 = −∆𝑈 = 𝑛 𝑅 𝑇" − 𝑇!
2

𝑓 𝑝" 𝑉" 𝑝! 𝑉!
=𝑛 𝑅 −
2 𝑛𝑅 𝑛𝑅

𝑝" 𝑉" − 𝑝! 𝑉!
=
2/𝑓

1
𝑊= 𝑝 𝑉 − 𝑝! 𝑉!
𝛾−1 " "

initial state final state

note that on the RHS the term is 𝑝% 𝑉% − 𝑝" 𝑉" , not 𝑝" 𝑉" − 𝑝% 𝑉%
Example Adiabatic compression in a diesel engine
A cylinder of a diesel engine contains air with 𝛾 = 1.400, initially at
1.01×10& Pa, 27 ℃ and initial volume 1.00 L. The air is compressed to 1⁄15.0 of its initial volume.

The final temperature and pressure are

#$"
𝑉" %.'
𝑇! = 𝑇" = 300 K 15.0
𝑉!
= 886 K

𝑉" #
𝑝! = 𝑝" = 1.01×10( Pa 15.0 ".'
𝑉!
= 44.8×10( Pa

Work done by the gas during the compression

1 ( ) (
0.001m)
𝑊= 1.01×10 Pa 0.001m − 44.8×10 Pa
1.400 − 1 15.0
= −494 J

note the sign of W

Question
If you compress an ideal gas to half of its initial volume, arrange the final
pressure in the following cases in descending order:
a) a monatomic gas compressed adiabatically
b) a monatomic gas compressed isothermally
c) a diatomic gas compressed adiabatically
d) a diatomic gas compressed isothermally
2 . Heat Transport
tures of water. One Celsius degree equals 5 Fahrenheit degrees. T1 p1 Conductor
(See Example 17.1.)
The Kelvin scale has its zero at the extrapolated zero-pressure … then systems A and B are in
temperature for a gas thermometer, - 273.15°C = 0 K. In the gas- thermal equilibrium with each other.
thermometer scale, the ratio of two temperatures T1 and T2 is defined
to be equal to the ratio of the two corresponding gas-thermometer
pressures p1 and p2 .
Thermal expansion
Thermal expansion and thermal stress: A temperature change ¢T ¢L = aL 0 ¢T (17.6) L 5 L 0 1 DL
causes a change in any linear dimension L 0 of a solid body. The 5 L 0 (1 1 a DT )
change ¢L is approximately proportional to L 0 and ¢T. Similarly, a T0
temperature change causes a change ¢V in the volume V0 of any solid ¢V = bV0 ¢T (17.8) L0 DL
or liquid; ¢V is approximately proportional to V0 and ¢T. The quanti- T0 1 DT
ties a and b are the coefficients of linear expansion and volume expan- F
= - Ya ¢T (17.12)
sion, respectively. For solids, b = 3a. (See Examples 17.2 and 17.3.) A
When a material is cooled or heated and held so it cannot contract
or expand, it is under a tensile stress F> A. (See Example 17.4.)

Assume
Heat, phase changes, a and
solid with length
calorimetry: 𝐿9 , 𝐿
Heat is energy in:transit respectively
, 𝐿; from and the
Q = mc ¢T volume
(17.13) Phaseischanges,
𝑉 =temperature
𝐿9 𝐿: 𝐿is ;constant:
one body to another as a result of a temperature difference. Equations Q 5 1mL
(17.13)The solidgive
and (17.18) expands
the quantity of heat Q required to cause a T (°C)

temperature change ∆T𝑉in< a= 𝐿9 of+material

quantity Δ𝐿9 with 𝐿:mass+ mΔ𝐿 and 𝐿 Q+= Δ𝐿 nC ¢T (17.18)
= 𝐿9 𝐿: 𝐿; 1100+ 𝛼Δ𝑇 =Boiling point
specific heat c (alternatively, with number of moles n and molar heat
: ; ;
capacity C ! Mc, where M is the molar mass and m ! nM). When Q = "mL (17.20) Melting point
0
heat isHence,
added to a the
body, change inwhen
Q is positive; volume is Q is
it is removed, t
negative. (See Examples 17.5 and 17.6.) <−𝑉
To change a mass m of a material toΔ𝑉 𝑉 phase Temperature rises, phase does not change:
a different at the same = − 1 ≈ 3𝛼Δ𝑇 Q 5 mc DT
=
temperature (such as liquid to vapor), a quantity of heat given by = 1 + 𝛼Δ𝑇
𝑉 𝑉
Eq. (17.20) must be added or subtracted. Here L is the heat of fusion,
vaporization, or sublimation. → 𝛽 = 3𝛼
In an isolated system whose parts interact by heat exchange, the
algebraic sum of the Q’s for all parts of the system must be zero. (See
Examples 17.7–17.10.)
 bowl by pouring very hot water into it; the thermal stress between the hot and
cold parts of the bowl exceeds the breaking stress of the glass, causing cracks.
The same phenomenon makes ice cubes crack when dropped into warm water.
Heat-resistant glasses such as Pyrex™ have exceptionally low expansion coeffi-
cients and high strength.
Example
Example 17.4 Thermal stress
An aluminum cylinder 10 cm long, with a cross-sectional area of exerts on the walls. We use Eq. (17.12) to relate F> A to the temper-
20 cm2, is used as a spacer between two steel walls. At 17.2°C it ature change ¢T, and from that calculate F. (The length of the
just slips between the walls. Calculate the stress in the cylinder and cylinder is irrelevant.) We find Young’s modulus YAl and the coeffi-
the total force it exerts on each wall when it warms to 22.3°C, cient of linear expansion aAl from Tables 11.1 and 17.1, respec-
assuming that the walls are perfectly rigid and a constant distance tively.
apart.
EXECUTE: We have YAl = 7.0 * 10 10 Pa and aAl = 2.4 *
10 -5 K -1, and ¢T = 22.3°C - 17.2°C = 5.1 C° = 5.1 K. From
SOLUTION Eq. (17.12), the stress is
IDENTIFY and SET UP: Figure 17.14 shows our sketch of the situa- F
tion. Our target variables are the thermal stress F> A in the cylinder, = -YAlaAl ¢T
A
whose cross-sectional area A is given, and the associated force F it = -17.0 * 10 10 Pa212.4 * 10 -5 K -1215.1 K2
= -8.6 * 106 Pa = -1200 lb>in.2
17.14 Our sketch for this problem. The total force is the cross-sectional area times the stress:
F
F = Aa b = 120 * 10 -4 m221-8.6 * 10 6 Pa2
A
= -1.7 * 10 4 N = 1.9 tons
EVALUATE: The stress on the cylinder and the force it exerts on
each wall are immense. Such thermal stresses must be accounted
for in engineering.

Test Your Understanding of Section 17.4 In the bimetallic strip shown in

Fig. 17.3a, metal 1 is copper. Which of the following materials could be used for metal 2?
(There may be more than one correct answer). (i) steel; (ii) brass; (iii) aluminum. ❙
change ¢L is approximately proportional to L 0 and ¢T. Similarly, a T0
temperature change causes a change ¢V in the volume V0 of any solid ¢V = bV0 ¢T (17.8) L0 DL
or liquid; ¢V is approximately proportional to V0 and ¢T. The quanti- T0 1 DT
ties a and b are the coefficients of linear expansion and volume expan- F
= -Ya ¢T (17.12)
sion, respectively. For solids, b = 3a. (See Examples 17.2 and 17.3.) A
When a material is cooled or heated and held so it cannot contract
Phase transition and latent heat
or expand, it is under a tensile stress F> A. (See Example 17.4.)

Heat, phase changes, and calorimetry: Heat is energy in transit from Q = mc ¢T (17.13) Phase changes, temperature is constant:
one body to another as a result of a temperature difference. Equations Q 5 1mL
T (°C)
(17.13) and (17.18) give the quantity of heat Q required to cause a
temperature change ∆T in a quantity of material with mass m and Q = nC ¢T (17.18)
100
Boiling point
specific heat c (alternatively, with number of moles n and molar heat
capacity C ! Mc, where M is the molar mass and m ! nM). When Q = "mL (17.20) Melting point
0
heat is added to a body, Q is positive; when it is removed, Q is t
negative. (See Examples 17.5 and 17.6.) Temperature rises, phase does not change:
To change a mass m of a material to a different phase at the same Q 5 mcDT
temperature (such as liquid to vapor), a quantity of heat given by
Eq. (17.20) must be added or subtracted. Here L is the heat of fusion,
vaporization, or sublimation.
In an isolated system whose parts interact by heat exchange, the
algebraic sum of the Q’s for all parts of the system must be zero. (See
Examples 17.7–17.10.)

The latent
Conduction, heatand
convection, is radiation:
relatedConduction
to the change of ofentropy of
is the transfer dQ the system
TH - TC during the Heatphasecurrent H
heat within materials without bulk motion of the materials. The heat H = = kA (17.21)
transition. (ref. to lecture 9)
current H depends on the area A through which the heat flows, the
dt L

length L of the heat-flow path, the temperature difference 1TH - TC2, TH A TC

4
and the thermal conductivity k of the material. (See Examples H = AesT (17.25) L
17.11–17.13.) TH 2 TC
Heat current H 5 kA
Convection is a complex heat-transfer process that involves mass L
Hnet = Aes1T 4 - T s42 (17.26)
motion from one region to another.
Radiation is energy transfer through electromagnetic radiation.
The radiation heat current H depends on the surface area A, the emis-
ciple is used in “seeding” clouds, which often contain supercooled water vapor,
to cause condensation and rain.
A liquid can sometimes be superheated above its normal boiling temperature.
Any small disturbance such as agitation causes local boiling with bubble formation.
Steam heating systems for buildings use a boiling–condensing process to
transfer heat from the furnace to the radiators. Each kilogram of water that is

Phase of water changes. During these periods, temperature stays 17.21 Graph of temperature versus time
constant and the phase change proceeds as heat is added: Q 5 1mL. for a specimen of water initially in the
T (°C) solid phase (ice). Heat is added to the
Ice melts to Liquid water vaporizes specimen at a constant rate. The tempera-
liquid water to steam at 100°C. ture remains constant during each change
125 at 0°C. of phase, provided that the pressure
d Boiling remains constant.
100 e point
75
50
25
b Melting
0 c point
a
225 Time
Ice warms. Liquid water warms. Steam warms.

Temperature of water changes. During these periods, temperature

rises as heat is added: Q 5 mc DT.
 need only Eq. (17.13). With subscripts C for coffee, W for water,
and Al for aluminum, we have T0C = 70.0° and T0Al = 20.0°;
Table 17.3 gives cW = 4190 J>kg # K and cAl = 910 J>kg # K.
EXECUTE: The (negative) heat gained by the coffee is Q C =
m CcW ¢TC. The (positive) heat gained by the cup is Q Al =
m AlcAl ¢TAl. We set Q C + Q Al = 0 (see Problem-Solving Strat-
Example
egy 17.2) and substitute ¢TC = T - T0C and ¢TAl = T - T0Al:
Example 17.8 Changes in both temperature and phase
A glass contains 0.25 kg of Omni-Cola (mostly water) initially at
25°C. How much ice, initially at - 20°C, must you add to obtain a
final temperature of 0°C with all the ice melted? Neglect the heat
capacity of the glass.
SOLUTION
IDENTIFY and SET UP: The Omni-Cola and ice exchange heat. The
cola undergoes a temperature change; the ice undergoes both a tem-
perature change and a phase change from solid to liquid. We use
subscripts C for cola, I for ice, and W for water. The target variable
is the mass of ice, m I. We use Eq. (17.13) to obtain an expression
for the amount of heat involved in cooling the drink to T = 0°C and
warming the ice to T = 0°C, and Eq. (17.20) to obtain an expres-
sion for the heat required to melt the ice at 0°C. We have T0C =
25°C and T0I = - 20°C, Table 17.3 gives cW = 4190 J> kg # K and
cI = 2100 J> kg # K, and Table 17.4 gives L f = 3.34 * 10 5 J>kg.
Example 17.9 What’s cooking?
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. Find
the final temperature of the pot and its contents, and determine the
phase of the water (liquid, gas, or a mixture). Assume that no heat
EVALUATE: The final temperature is much closer to the initial tem-
perature of the coffee than to that of the cup; water has a much
higher specific heat than aluminum, and we have more than twice
as much mass of water. We can also find the quantities of heat by
substituting the value T = 66.0°C back into the original equations.
We find Q C = - 5.0 * 10 3 J and Q Al = + 5.0 * 10 3 J . As
expected, Q C is negative: The coffee loses heat to the cup.
EXECUTE: From Eq. (17.13), the (negative) heat gained by the
Omni-Cola is Q C = m CcW ¢TC. The (positive) heat gained by the
ice in warming is Q I = m IcI ¢TI. The (positive) heat required to
melt the ice is Q 2 = m IL f. We set Q C + Q I + Q 2 = 0, insert
¢TC = T - T0C and ¢TI = T - T0I, and solve for m I:
m CcW ¢TC + m IcI ¢TI + m IL f = 0
m CcW1T - T0C2 + m IcI1T - T0I2 + m IL f = 0
mI3cI1T - T0I2 + Lf4 = - mCcW1T - T0C2
cW1T0C - T2
mI = mC
cI1T - T0I2 + L f
Substituting numerical values, we find that m I = 0.070 kg = 70 g.
EVALUATE: Three or four medium-size ice cubes would make
about 70 g, which seems reasonable given the 250 g of Omni-Cola
to be cooled.
EXECUTE: First consider case (1), which parallels Example 17.8
exactly. The equation that states that the heat flow into the water
equals the heat flow out of the pot is
Q W + Q Cu = m WcW1T - T0W2 + m CucCu1T - T0Cu2 = 0
 nM). When Q = "mL (17.20) Melting point
0
ed, Q is t
Temperature rises, phase does not change:
se at the
Heatsame
Conduction Q 5 mcDT
at given by
• Conduction is the transfer of heat within materials without bulk motion of the
heat of fusion,
materials.
• The heat current 𝑯 [𝐽/𝑠 = 𝑊] depends on the area 𝐴 through which the heat flows,
xchange,the thelength 𝐿 of the heat-flow path, the temperature difference 𝑇> − 𝑇? and the
st be zero.thermal
(See conductivity 𝑘 of the materials.
𝑑𝑄 𝑇> − 𝑇@
𝐻= = 𝑘𝐴
𝑑𝑡 𝐿

If the temperature
e transfer• of dQ varies inTaHnonuniform
- TC Heat current H
way along
ials. The heat = length=of kA
Hthe the conducting(17.21)
rod,
dt
𝑑𝑄 𝑑𝑇 L
at flows, the 𝐻= = −𝑘𝐴
𝑑𝑡 𝑑𝑥
ce 1TH - TC2, TH A TC
amples H = AesT 4 temperature gradient
(17.25) L
TH 2 TC
Heat current H 5 kA
involves mass L
Hnet = Aes1T 4 - T s42 (17.26)
 1. If heat flows through a single object, use Eq. (17.21) to solve use distances in meters, heat in joules, and T in kelvins.
for the target variable.
2. If the heat flows through two different materials in succession EVALUATE your answer: Are the results physically reasonable?
(in series), the temperature T at the interface between them is

Example Example 17.11 Conduction into a picnic cooler

A Styrofoam cooler (Fig. 17.24a) has total wall area (including the EXECUTE: We assume that the total heat flow is the same as it
lid) of 0.80 m2 and wall thickness 2.0 cm. It is filled with ice, would be through a flat Styrofoam slab of area 0.80 m2 and thick-
water, and cans of Omni-Cola, all at 0°C. What is the rate of heat ness 2.0 cm = 0.020 m (Fig. 17.24b). We find k from Table 17.5.
flow into the cooler if the temperature of the outside wall is 30°C? From Eq. (17.21),
How much ice melts in 3 hours?
TH - TC
= 10.027 W>m # K210.80 m22
30°C - 0°C
H = kA
L 0.020 m
SOLUTION
= 32.4 W = 32.4 J>s
IDENTIFY and SET UP: The target variables are the heat current H
and the mass m of ice melted. We use Eq. (17.21) to determine H
and Eq. (17.20) to determine m.

17.7 Mechanisms of Heat Transfer 573

The total heat flow is Q ! Ht, with t ! 3 h ! 10,800 s. From Table 17.24 Conduction of heat across the walls of a Styrofoam cooler.
17.4, the heat of fusion of ice is L f ! 3.34 * 10 5 J>kg, so from
(a) A cooler at the beach (b) Our sketch for this problem
Eq. (17.20) the mass of ice that melts is
Q 132.4 J>s2110,800 s2
m = = = 1.0 kg
Lf 3.34 * 105 J>kg

EVALUATE: The low heat current is a result of the low thermal con-
ductivity of Styrofoam.

Example 17.12 Conduction through two bars I

A steel bar 10.0 cm long is welded end to end to a copper bar 20.0 cm 17.25 Our sketch for this problem.
long. Each bar has a square cross section, 2.00 cm on a side. The
Example Example 17.12 Conduction through two bars I
A steel bar 10.0 cm long is welded end to end to a copper bar 20.0 cm 17.25 Our sketch for this problem.
long. Each bar has a square cross section, 2.00 cm on a side. The
free end of the steel bar is kept at 100°C by placing it in contact
with steam, and the free end of the copper bar is kept at 0°C by
placing it in contact with ice. Both bars are perfectly insulated on
their sides. Find the steady-state temperature at the junction of the
two bars and the total rate of heat flow through the bars.

SOLUTION
IDENTIFY and SET UP: Figure 17.25 shows the situation. The heat
currents in these end-to-end bars must be the same (see Problem- Substituting L S = 10.0 cm and L Cu = 20.0 cm, the given values
Solving Strategy 17.3). We are given “hot” and “cold” tempera- of TH and TC, and the values of k S and k Cu from Table 17.5, we find
tures TH = 100°C and TC = 0°C. With subscripts S for steel and T = 20.7°C.
Cu for copper, we write Eq. (17.21) separately for the heat currents We can find the total heat current by substituting this value of T
HS and HCu and set the resulting expressions equal to each other. into either the expression for HS or the one for HCu:
EXECUTE: Setting HS = HCu, we have from Eq. (17.21)
HS = 150.2 W>m # K210.0200 m22
100°C - 20.7°C
TH - T T - TC 0.100 m
HS = k S A = HCu = k Cu A = 15.9 W
LS L Cu
HCu = 1385 W>m # K210.0200 m22
20.7°C
We divide out the equal cross-sectional areas A and solve for T: = 15.9 W
0.200 m
kS k Cu
TH + TC EVALUATE: Even though the steel bar is shorter, the temperature
LS L Cu
T = drop across it is much greater (from 100°C to 20.7°C) than across
kS k Cu the copper bar (from 20.7°C to 0°C). That’s because steel is a
a + b
LS L Cu much poorer conductor than copper.

Example 17.13 Conduction through two bars II

Suppose the two bars of Example 17.12 are separated. One end of 17.26 Our sketch for this problem.
each bar is kept at 100°C and the other end of each bar is kept at
0°C. What is the total heat current in the two bars?
 TH - TC TH
H = HS + HCu = k S A + k Cu A
LS

= 150.2 W>m # K210.0200 m22

100 K
0.100 m
+ 1385 W>m # K210.0200 m22
100 K
0.200 m
= 20.1 W + 77.0 W = 97.1 W

Heat Convection
Conv
Conv
• a complex heat-transfer process that involves mass motion from 17.27 A heating element in the tip of
this submerged tube warms the surround- space
ing water, producing a complex pattern of
one region to another free convection.
syste
body.
conve
• no simple equation sion,

• The heat current due to convection is proportional to the surface vectio

Fr
daily
area 𝐴 mech
F mal u

𝐻≈𝐴 𝑇− 𝑇ABCDE G fer w

vario
pump
Co
equat
1.

2.

17.28 This false-color infrared photo-

graph reveals radiation emitted by various
parts of the man’s body. The strongest
emission (colored red) comes from the
warmest areas, while there is very little 3.
emission from the bottle of cold beverage.

Radi
Radi
infrar
ation
Most
conve
even
Heat Radiation
• Radiation is energy transfer through electromagnetic radiation.
• The radiation heat current 𝐻 depends on the surface area 𝐴, the emissivity 𝑒 of the
surface (a pure number between 0 and 1), the Kelvin temperature 𝑇, and the Stefan-
Boltzmann constant 𝜎 = 5.67×10$H 𝑊𝑚$! 𝐾 $G . (We will come back to this formula
in modern physics)

𝐻 = 𝐴𝑒𝜎𝑇 G

• 𝑒 = 1 is the perfect blackbody.

• The net radiation heat current 𝐻IJK from a body at temperature 𝑇 to its surroundings
at temperature 𝑇L is
𝐻 = 𝐴𝑒𝜎 𝑇 G − 𝑇LG
Heat Radiation
• When a body at temperature 𝑇 is radiating, its surroundings at temperature 𝑇L are also
radiating, and the body absorbs some of this radiation.
• In thermal equilibrium (𝑇 = 𝑇L ),
𝐻MNOPNKPQI = 𝐻NRLQMSKPQI → 𝐻NRQLMSKPQI = 𝐴𝑒𝜎𝑇LG

• The net radiation heat current 𝐻IJK from a body at temperature 𝑇 to its surroundings
at temperature 𝑇L is
𝐻 = 𝐴𝑒𝜎 𝑇 G − 𝑇LG

𝐻MNOPNKPQI

environment body
𝐻LRLQMSKPQI
ature T with surroundings at temperature Ts is

Hnet = AesT 4 - AesT s4 = Aes1T 4 - T s42 (17.26)

In this equation a positive value of H means a net heat flow out of the body.
Equation (17.26) shows that for radiation, as for conduction and convection, the
Example
heat current depends on the temperature difference between two bodies.

Example 17.15 Radiation from the human body

What is the total rate of radiation of energy from a human body with
surface area 1.20 m2 and surface temperature 30°C = 303 K? If
the surroundings are at a temperature of 20°C, what is the net rate of
radiative heat loss from the body? The emissivity of the human body
is very close to unity, irrespective of skin pigmentation.
576 CHAPTER 17 Temperature and Heat
SOLUTION
IDENTIFY and SET UP: We must consider both the radiation that
the body emits and the radiation that it absorbs from its surround-
ings. Equation (17.25) gives the rate of radiation of energy from
the body, and Eq. (17.26) gives the net rate of heat loss.
Continued

EXECUTE: Taking e = 1 in Eq. (17.25), we find that the body radi- Hnet = Aes1T 4 - T s42
= 11.20 m2211215.67 * 10-8 W>m2 # K4231303 K24
ates at a rate
H = AesT 4 - 1293 K244 = 72 W
= 11.20 m2211215.67 * 10 -8 W>m2 # K421303 K24 = 574 W
EVALUATE: The value of Hnet is positive because the body is losing
This loss is partly offset by absorption of radiation, which depends heat to its colder surroundings.
on the temperature of the surroundings. From Eq. (17.26), the net
rate of radiative energy transfer is

Applications of Radiation
Heat transfer by radiation is important in some surprising places. A premature
baby in an incubator can be cooled dangerously by radiation if the walls of
the incubator happen to be cold, even when the air in the incubator is warm. Some
incubators regulate the air temperature by measuring the baby’s skin temperature.

FigureExample
P17.125
6.00
r5 4.00 cm
2.00 cm cm
Steam pipe
Cork
Styrofoam
emperature at a radius of 4.00 cm,
meet? (b) What is the total rate of
length of pipe? (Hint: Use the
Challenge Problem 17.124.)
hange in a Clock. A pendulum
econd on each side-to-side swing
omplete period). (a) Will a pendu-
ather and lose it in cold, or the
(b) A particular pendulum clock
e pendulum shaft is steel, and its
with that of the bob. What is the
of the shaft when it is cooled to
per day will the clock gain or lose
t the temperature be controlled if
more than 1.00 s a day? Does the
he pendulum?
Answers 589
17.127 ... BIO A Walk in the Sun. Consider a poor lost soul
walking at 5 km>h on a hot day in the desert, wearing only a
bathing suit. This person’s skin temperature tends to rise due to
four mechanisms: (i) energy is generated by metabolic reactions in
the body at a rate of 280 W, and almost all of this energy is con-
verted to heat that flows to the skin; (ii) heat is delivered to the skin
by convection from the outside air at a rate equal to
k¿Askin1Tair - Tskin2, where k¿ is 54 J>h # C° # m2, the exposed skin
area Askin is 1.5 m2, the air temperature Tair is 47°C, and the skin
temperature Tskin is 36°C; (iii) the skin absorbs radiant energy
from the sun at a rate of 1400 W>m2; (iv) the skin absorbs radiant
energy from the environment, which has temperature 47°C.
(a) Calculate the net rate (in watts) at which the person’s skin is
heated by all four of these mechanisms. Assume that the emissivity
of the skin is e = 1 and that the skin temperature is initially 36°C.
Which mechanism is the most important? (b) At what rate
(in L>h2 must perspiration evaporate from this person’s skin to
maintain a constant skin temperature? (The heat of vaporization of
water at 36°C is 2.42 * 106 J>kg.2 (c) Suppose instead the person
is protected by light-colored clothing 1e L 02 so that the exposed
skin area is only 0.45 m2. What rate of perspiration is required
now? Discuss the usefulness of the traditional clothing worn by
desert peoples.
 (c) To avoid possible confusion, denote the pendulum period by τ . For this problem,
∆τ = 1 ∆L = 6.0 × 10−5 so in one day the clock will gain (86,400 s)(6.0 × 10−5 ) = 5.2 s.
τ 2 L
∆τ 1 ∆τ 1.0 s
(d) = 2 α∆T . = gives ∆T = 2[(1.2 × 10−5 (C°) −1)(86,400)]−1 = 1.9 C°. T must be
τ τ 86,400 s
Example controlled to within 1.9 C°.
EVALUATE: In part (d) the answer does not depend on the period of the pendulum. It depends only on the
fractional change in the period.
17.127. IDENTIFY: The rate in (iv) is given by Eq. (17.26), with T = 309 K and Ts = 320 K. The heat absorbed in
the evaporation of water is Q = mL.
m
SET UP: m = ρV , so = ρ.
V
EXECUTE: (a) The rates are: (i) 280 W,
(ii) (54 J/h ⋅ C° ⋅ m 2 )(1.5 m 2 )(11 C°)/(3600 s/h) = 0.248 W,
(iii) (1400 W/m 2 )(1.5 m 2 ) = 2.10 × 103 W,
(iv) (5.67 × 10−8 W/m 2 ⋅ K 4 )(1.5 m 2 )((320 K)4 − (309 K)4 ) = 116 W.
The total is 2.50 kW, with the largest portion due to radiation from the sun.
P 2.50 × 103 W
(b) = = 1.03 × 10−6 m3/s. This is equal to 3.72 L/h.
ρ Lv (1000 kg/m )(2.42 × 10 J/kg ⋅ K)
3 6

(c) Redoing the above calculations with e = 0 and the decreased area gives a power of 945 W and a
corresponding evaporation rate of 1.4 L/h. Wearing reflective clothing helps a good deal. Large areas of
loose-weave clothing also facilitate evaporation.
EVALUATE: The radiant energy from the sun absorbed by the area covered by clothing is assumed to be
zero, since e ≈ 0 for the clothing and the clothing reflects almost all the radiant energy incident on it. For
the same reason, the exposed skin area is the area used in Eq. (17.26).
3. Phase transition
factors, such as pressure, can also affect a phase transition
besides temperature.
The phase diagram show
Phase the phases
diagram of 𝐻X (solid,
𝑂 liquid, gas)
as a function of T and P

liquid/gas coexistence
(evaporation)
solid/liquid/gas
coexistence
Solid/gas
coexistence(sublimation)

A phase transition is a “discontinuous” change in the properties of a substance when its

Theenvironment
lines inchanges
the infinitesimally.
phase diagram indicate the conditions
that two phases can coexist in equilibrium. (See “dry ice
bomb” in YouTube.)
§ The lines in the phase diagram indicate the conditions that two phases can coexist in
equilibrium. (See “dry ice bomb” in YouTube.)
§ In the regions separated by the phase lines, respectively, ice, water and steam are the most
stable phases.
§ However, “metastable” phases can still exist.
§ Example: “supercooled” water can exist at the left of the solid/liquid coexistence line.
§ Example: “Superheated” water can exist at the right of the liquid/gas coexistence line.
§ See “superheating” and “supercooling” in YouTube.
 Phase diagram of 𝐻X 𝑂 Phase diagram of 𝐶𝑂X

• the slope of the solid-liquid boundary are different

• For H2O, the solid-liquid boundary, actually has a negative slope (melting temperature
decreases with increasing pressure), which is unusual.
• Water expands when it freezes (-> ice floats)
 Vapor pressure

• At the phase boundary between liquid and gas, the liquid coexists at some
temperature with gas at an appropriate pressure called the vapour pressure.
• At higher temperature, a greater pressure must be applied to keep the liquid and
gas in coexistence
• At higher pressure, the gas becomes more dense
• At the critical point, the liquid and dense gas becomes indistinguishable - then we
call the system a fluid. (See “critical point of benzene” in YouTube.)
Unusual phase diagram of helium isotopes: 4He and 3He

• Helium is the only element that remains liquid at 0 K

• Helium will form solid, but only at high pressure
• Helium has two distinct liquid phase
• normal liquid (He I)
• superfluid (He II)→zero viscosity, very high thermal conductivity, etc.
Different phase diagram

At low B, T, the superconducting phase has zero Magnetic moments point up or down, depending upon
electrical resistance the direction of the applied B field. Moments also
disappear at the critical point when T is raised.
4. Van der Waals equation
Van der Waals model
• the ideal gas law 𝑃𝑉 = 𝑛𝑅𝑇 can only describe non-interacting (or dilute) gas
• The van der Waals equation is a modification of the ideal gas law that takes molecular
interaction into account
𝑎𝑁 !
𝑃+ ! 𝑉 − 𝑁𝑏 = 𝑁𝑘𝑇
𝑉

• 𝑁𝑏 is a “volume correction”. Each molecule has a volume b. The available volume is

the total volume minus all of the molecular volume (Nb). The fluid cannot be
compressed to zero volume --- It can be compressed only until all molecules are
touching (𝑉 = 𝑁𝑏). Then the pressure goes to infinity.
NT'
• is a “pressure correction”. If the molecules have an attractive interaction (like a
U'
stretched spring), then the molecule will be “pulled back” when it tries to collide
with the wall. This means the pressure will be less than that of the ideal gas.
 Van der Waals model

• The interaction energy of a molecule is proportional to the number of its neighbors.

𝑁 -ve sign is due to the attractive
𝜖PIK ∝ −
𝑉 nature of interaction

NT'
• Total interaction energy 𝑈PIK = 𝑁𝜖PIK = −
U

• Since Δ𝑈 = −∫ 𝑃𝑑𝑉, the pressure correction due to the interaction energy is

𝑑𝑈PIK 𝑎𝑁 !
𝑃PIK = − =− !
𝑑𝑉 𝑉

• The constants 𝑎 and 𝑏 depend upon the substance

• This equation is applicable to fluids (liquids and gases) and can be used to describe the
liquid-gas transition
 V Nb V

Each line in the figure corresponds to a given temperature

(isotherm)
Equation of State High T

Low T

solution ① ② ③

rd
The van der Vaals
𝑁𝑘𝑇equation
𝑎𝑁 !is a 3 order polynomial in V
(a) when𝑃T=is very high− !
𝑉 − 𝑁𝑏 𝑉
rd
• The van der Waals is a 3 order polynomial in 𝑉2
NkT aN The first term is much
• when 𝑇 is very high, P
larger than the second term
V Nb V2
𝑁𝑘𝑇
𝑃≈NkT𝑉 − 𝑁𝑏 This is single valued (it looks
• when 𝑇 is small, there are 3 solutions
V Nb of 𝑉 for every (𝑇, 𝑃). like the ideal gas law)
approximately
OV
• However, the region with +ve slope ( > 0) in unstable. Why?
(b) when T is small,OUthere are 3 solutions of V for every
(T,P)
V can have 3 values for every P (see the figure above)
(the curve takes a different shape)
Physical picturePhysical Picture
the triangular loop in the graph (2-3-4-5-6) represents
• unstable
the triangular loop in thestates
graph (2-3-4-5-6) represents unstable states
• when the gas iswhen the gas is compressed at constant temperature, it
compressed at constant temperature, it will move directly between
will move directly between points 0-1-2-6-7-8 (not, -3-4-
points 0-1-2-6-7-85-)(not -3-4-5-)
• the pressure willthe
risepressure
continuously during compression;
will rise continuously the volume will drop between
during compression;
points 2-6 duringthe volume willwith
compression drop between in
no change points 2-6 during
pressure
compression with no change in pressure
• points 3,4,5 will points
not be3,4,5
realized
will not be realized

Phase transition
gas 0
+ gas
liquid
mixture
liquid

From 0-2 is a continuous change. Volume decreases rapidly

with increasing pressure. This is a property of a
gas.
 For both phases independently, the equation of s
continuous, with continuous derivatives. Howeve
function “abruptly” changes to the other function
Gibbs enthalpy. Phase transitions in the P
Physical picture
Physical Picture Gibbs enthalpy G(T, P, N ), as defined by (5.11), w
the triangular loop in the graph (2-3-4-5-6) representsP and of the temperature T . G(T, P, N ) changes c
unstable states
• From 0-2 is a continuous change. Volume decreases rapidly whenwith
theincreasing pressure
transition is of- first
gas order. The entropy
when the gas is compressed at constant temperature, it
• From 2-6 is a discontinuous change. Pressure is constant and volume decreases (gas turns into liquid). This
will move directly between points 0-1-2-6-7-8 (not, -3-4-the derivatives
is a first order transition, where liquid and gas coexist at the vapor pressure.
5-) ⇤The system
⌅ is an ⇤ ⌅
inhomogeneous mixture of gas andduring
liquid.compression;
As the total volume is decreased ⇥G points 2 and 6, the
between ⇥G
the pressure will rise continuously S = , V = ,
fraction of liquid increases and the fraction
the volume will drop between points 2-6 during of gas decreases. ⇥T P ⇥P T
From 6-8 is with
• compression a continuous
no change change. Volume decreases slowly with increasing pressure - liquid.
in pressure
of the Gibbs potential, are in contrast discontinuo
points 3,4,5 will not be realized

Phase transition
gas 0
+ gas
liquid 6
mixture
liquid

From 0-2 is a continuous change. Volume decreases rapidly

with increasing pressure. This is a property of aLatent heat. Let us consider an instead of the
gas. projection of the equation of state for water.
Maxwell’s Construction
• We expect that the work done from 2 to 6 should be the same following the van der
Waals equation and the constant pressure line,
Area 2-3-4 = Area 4-5-6
• The transformation pressure can be found by moving a straight line until the two
The transformation pressure can be found by moving a
areas are equal. This is called the Maxwell’s construction.
straight line until the two areas are equal. This is called
• The vapour pressure is thethepressure
Maxwell’sat that particular temperature.
construction.
The vapour pressure is the pressure at that particular
temperature.
Same area
8

gas 0
+ gas
liquid
mixture
liquid

At low T, the gas undergoes a phase transition to a liquid as

it is compressed at constant T. At the transition pressure the
gas and liquid coexist.
 gas 0
+ gas
liquid
mixture
liquid

• At low T, the gas undergoes a phase transition to a liquid as it is compressed at

constant T. At the transition pressure the gas and liquid coexist.
At low T, the gas undergoes a phase transition to a liquid as
• At high T, there is no distinction between gas and liquid. It is a “fluid”.
it is compressed at constant T. At the transition pressure the
gas and liquid coexist.
P fluid
P liquid
gas+liquid
gas
Transition P
low T high T
V V

At high T, there is no distinction between gas and liquid. It

is a “fluid”.
Repeating this exercise for many temperatures and reading
• Repeating this exercise for many temperatures and reading off the transition pressure for
each temperature, we get the following diagrams
P/Pc P/Pc
T8
T8
T7
P6 T7 P6
T6 = Tc
P5 T6=Tc P5
P4 P4
T5
P3 T5 P3
P2 P2 T4
P1 T4 P1 T3
T3
T2
T1
T2
T1
V/Vc
T/Tc

• Above the critical temperature, Tc, the phase boundary between liquid and gas does not
exist, and there is nothe
Above phase transition.
critical The vapor
temperature, Tc, thepressure at Tc is called
phase boundary the critical
between
pressure, Pc. The corresponding
liquid and gas does notvolume
exist, at
andTcthere
and Pisc no
is called the critical
phase transition. volume, Vc . Tc, Vc,
The
Pc define the critical
vapour point where
pressure at Tthe
c isphase
calledboundary
the criticalends
pressure, Pc. The
corresponding volume at Tc and Pc is called the critical volume, Vc
. Tc, Vc, Pc define the critical point where the phase boundary ends.
 Q: How to calculate Vc . Tc, Pc from the Van der Waals equation?

𝑎𝑁 !
𝑃+ ! 𝑉 − 𝑁𝑏 = 𝑁𝑘𝑇
𝑉
⇒ 𝑃𝑉 = − (𝑏𝑃𝑁 + 𝑁𝑘𝑇)𝑉 ! + 𝑎𝑁 ! 𝑉 − 𝑎𝑏𝑁 = = 0
is a cubic equation of 𝑉.
Triple roots
Since the critical point is the triple roots of the cubic equation,
(𝑇W , 𝑉W , 𝑃W )
the cubic equation at 𝑃 = 𝑃W and 𝑇 = 𝑇W can be P/P c P
rewritten as T8
T8
T7

𝑃W 𝑉 − 𝑉W = =0 P6 T7 T6 = Tc
P6

P5 T6=Tc P5
P4 P4
P3 T5 P3
P2 P2
P1 T4 P1
T3

T2
T1
V/Vc

Above the critical temperature, Tc, the phase b

By expanding the equation and comparing the coefficients, we can solve 3 unknowns
(𝑇W , 𝑃W , 𝑉W ):

8𝑎
𝑇W =
27𝑏𝑘
𝑎
𝑃W =
27𝑏 !

𝑉W = 3𝑏𝑁