Chapter 18 Heat and the First Law of Thermodynamics

Conceptual Problems
3 The specific heat of aluminum is more than twice the specific heat of copper. A block of copper and a block of aluminum have the same mass and temperature (20C). The blocks are simultaneously dropped into a single calorimeter containing water at 40C. Which statement is true when thermal equilibrium is reached? (a) The aluminum block is at a higher temperature than the copper block. (b) The aluminum block has absorbed less energy than the copper block. (c) The aluminum block has absorbed more energy than the copper block. (d) Both (a) and (c) are correct statements. Picture the Problem We can use the relationship Q = mcT to relate the amount of energy absorbed by the aluminum and copper blocks to their masses, specific heats, and temperature changes. Express the energy absorbed by the aluminum block: Express the energy absorbed by the copper block: Divide the second of these equations by the first to obtain: Because the blocks masses are the same and they experience the same change in temperature:

QAl = mAlcAl T
QCu = mCu cCu T
QCu mCu cCu T = QAl mAlcAl T QCu cCu = <1 QAl cAl

or QCu < QAl and (c) is correct.

11 A real gas cools during a free expansion, while an ideal gas does not cool during a free expansion. Explain the reason for this difference. Determine the Concept Particles that attract each other have more potential energy the farther apart they are. In a real gas the molecules exert weak attractive forces on each other. These forces increase the internal potential energy during an expansion. An increase in potential energy means a decrease in kinetic energy, and a decrease in kinetic energy means a decrease in translational kinetic energy. Thus, there is a decrease in temperature.

363

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Chapter 18

21 An ideal gas in a cylinder is at pressure P and volume V. During a quasi-static adiabatic process, the gas is compressed until its volume has decreased to V/2. Then, in a quasi-static isothermal process, the gas is allowed to expand until its volume again has a value of V. What kind of process will return the system to its original state? Sketch the cycle on a graph. Determine the Concept During a reversible adiabatic process, PV is constant, where < 1 and during an isothermal processes PV is constant. Thus, the pressure rise during the compression is greater than the pressure drop during the expansion. The final process could be a constant volume process during which heat is absorbed from the system. A constant-volume cooling will decrease the pressure and return the gas to its original state.

P
isothermal

adiabatic constant volume

Vf = 1 Vi 2

Vi

Estimation and Approximation

25 A typical microwave oven has a power consumption of about 1200 W. Estimate how long it should take to boil a cup of water in the microwave assuming that 50% of the electrical power consumption goes into heating the water. How does this estimate correspond to everyday experience? Picture the Problem Assume that the water is initially at 30C and that the cup contains 200 g of water. We can use the definition of power to express the required time to bring the water to a boil in terms of its mass, heat capacity, change in temperature, and the rate at which energy is supplied to the water by the microwave oven.

Use the definition of power to relate the energy needed to warm the water to the elapsed time:

P=

W mcT mcT = t = t t P

Substitute numerical values and evaluate t:

kJ (100C 30C ) kg K t = = 97.63 s 1.6 min , 600 W an elapsed time that seems to be consistent with experience. (0.200 kg ) 4.184

Heat and the First Law of Thermodynamics

365

Heat Capacity, Specific Heat, Latent Heat

29 How much heat must be absorbed by 60.0 g of ice at 10.0C to transform it into 60.0 g of water at 40.0C? Picture the Problem We can find the amount of heat that must be absorbed by adding the heat required to warm the ice from 10.0C to 0C, the heat required to melt the ice, and the heat required to warm the water formed from the ice to 40.0C.

Express the total heat required: Substitute for each term to obtain:

Q = Qwarm ice + Qmelt ice + Qwarm water

Q = mcice Tice + mLf + mcwater Twater = m(cice Tice + Lf + cwater Twater )

Substitute numerical values (See Tables 18-1 and 18-2) and evaluate Q:
kJ kJ (0C ( 10.0C )) + 333.5 Q = (0.0600 kg ) 2.05 kg K kg kJ (40.0C 0C ) + 4.184 kg K = 31.3 kJ

Calorimetry
33 While spending the summer on your uncles horse farm, you spend a week apprenticing with his farrier (a person who makes and fits horseshoes). You observe the way he cools a shoe after pounding the hot, pliable shoe into the correct size and shape. Suppose a 750-g iron horseshoe is taken from the farriers fire, shaped, and at a temperature of 650C, dropped into a 25.0-L bucket of water at 10.0C. What is the final temperature of the water after the horseshoe and water arrive at equilibrium? Neglect any heating of the bucket and assume the specific heat of iron is 460 J/(kg K) . Picture the Problem During this process the water will gain energy at the expense of the horseshoe. We can use conservation of energy to find the equilibrium temperature. See Table 18-1 for the specific heat of water.

366

Chapter 18

Apply conservation of energy to obtain:

Q
i

= Qwarm the water + Qcool the horseshoe = 0

or

mwater c water (t f 10.0C ) + mFe cFe (t f 650C ) = 0

Solve for tf to obtain:

tf = mwater c water (10.0C ) + mFe cFe (650C ) mwater c water + mFe cFe

Substitute numerical values and evaluate tf:

(25.0 kg ) 4.184 kJ kJ (650C ) (10.0C ) + (0.750 kg ) 0.460 kg K kg K kJ kJ + (0.750 kg ) 0.460 kg K kg K

tf =

(25.0 kg ) 4.184

= 12.1C

37 A 200-g piece of ice at 0C is placed in 500 g of water at 20C. This system is in a container of negligible heat capacity and is insulated from its surroundings. (a) What is the final equilibrium temperature of the system? (b) How much of the ice melts? Picture the Problem Because we can not tell, without performing a couple of calculations, whether there is enough heat available in the 500 g of water to melt all of the ice, well need to resolve this question first. See Tables 18-1 and 18-2 for specific heats and the latent heat of fusion of water.

(a) Determine the energy required to melt 200 g of ice:

kJ Qmelt ice = mice Lf = (0.200 kg ) 333.5 kg = 66.70 kJ

The energy available from 500 g of water at 20C is: kJ (0C 20C ) Qavailable, max = mwater c water Twater = (0.500 kg ) 4.184 kg K = 41.84 kJ Because Qavailable, max < Qmelt ice : The final temperature is 0C.

Heat and the First Law of Thermodynamics (b) Equate the energy available from the water Qavailable, max to miceLf and solve for mice to obtain: Substitute numerical values and evaluate mice:
mice = 41.84 kJ = 125 g kJ 333.5 kg

367

mice =

Qavailable, max Lf

43 A 100-g piece of copper is heated in a furnace to a temperature tC. The copper is then inserted into a 150-g copper calorimeter containing 200 g of water. The initial temperature of the water and calorimeter is 16.0C, and the temperature after equilibrium is established is 38.0C. When the calorimeter and its contents are weighed, 1.20 g of water are found to have evaporated. What was the temperature tC? Picture the Problem We can find the temperature t by applying conservation of energy to this calorimetry problem. See Tables 18-1 and 18-2 for specific heats and the heat of vaporization of water.

Use conservation of energy to obtain:

Q
i

= Qvaporize + Qwarm
water

the water

+ Qwarm the + Qcool the = 0

calorimeter Cu sample

or

mH 2 O, vaporized Lf, w + mH 2 O cH 2 O TH 2 O + mcal ccal Tw + mCu cCu TCu = 0

Substituting numerical values yields:

(1.20 g ) 2257

kJ kJ + (200 g ) 4.184 (38.0C 16.0C ) kg K kg K

kJ kJ (38.0C 16.0C ) + (100 g ) 0.386 (38.0C t C ) = 0 + (150 g ) 0.386 kg K kg K

Solving for tC yields:

t C = 618C

Work and the PV Diagram for a Gas

51 The gas is first cooled at constant volume until it reaches its final pressure. It is then allowed to expand at constant pressure until it reaches its final volume. (a) Illustrate this process on a PV diagram and calculate the work done by the gas. (b) Find the heat absorbed by the gas during this process.

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Chapter 18

Picture the Problem We can find the work done by the gas during this process from the area under the curve. Because no work is done along the constant volume (vertical) part of the path, the work done by the gas is done during its isobaric expansion. We can then use the first law of thermodynamics to find the heat absorbed by the gas during this process

(a) The path from the initial state (1) to the final state (2) is shown on the PV diagram.

P, atm 3.00 2.00 1.00 0 V, L 1

1.00

2.00

3.00

The work done by the gas equals the area under the curve:
101.325 kPa 10 3 m 3 Wby gas = PV = (2.00 atm )(2.00 L ) = 2.00 atm 2.00 L L atm = 405 J (b) The work done by the gas is the negative of the work done on the gas. Apply the first law of thermodynamics to the system to obtain: Substitute numerical values and evaluate Qin:
Qin = Eint Won

= (Eint,2 Eint,1 ) ( Wby gas ) = (Eint,2 Eint,1 ) + Wby gas

Qin = (912 J 456 J ) + 405 J = 861J

An ideal gas initially at 20C and 200 kPa has a volume of 4.00 L. It 57 undergoes a quasi-static, isothermal expansion until its pressure is reduced to 100 kPa. Find (a) the work done by the gas, and (b) the heat absorbed by the gas during the expansion.

Heat and the First Law of Thermodynamics

Picture the Problem The PV diagram shows the isothermal expansion of the ideal gas from its initial state 1 to its final state 2. We can use the ideal-gas law for a fixed amount of gas to find V2 and then evaluate PdV for an

369

P, kPa 200 1

isothermal process to find the work done by the gas. In Part (b) of the problem we can apply the first law of thermodynamics to find the heat added to the gas during the expansion. (a) Express the work done by a gas during an isothermal process: Apply the ideal-gas law for a fixed amount of gas undergoing an isothermal process: Substitute numerical values and evaluate V2:

100

2 293 K

4.00

V2

V, L

Wby gas = PdV = nRT

V1

V2

V2

2 dV dV = PV1 1 V V V1 V1

PV1 = P2V2 V2 = 1

P 1 V1 P2

V2 =

200 kPa (4.00 L ) = 8.00 L 100 kPa

Substitute numerical values and evaluate W:

Wby gas = (200 kPa )(4.00 L )
8.00 L

dV 8.00 L = (800 kPa L )[ln V ]4.00 L V 4.00 L

10 3 m 3 8.00 L = (800 kPa L ) ln = 554.5 kPa L L 4.00 L = 555 J (b) Apply the first law of thermodynamics to the system to obtain:
Qin = Eint Won

or, because Eint = 0 for an isothermal process, Qin = Won Qin = ( Wby gas ) = Wby gas = 555 J

Because the work done by the gas is the negative of the work done on the gas:

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Chapter 18

Remarks: in an isothermal expansion the heat added to the gas is always equal to the work done by the gas (Eint = 0).

Heat Capacities of Gases and the Equipartition Theorem

59 The heat capacity at constant pressure of a certain amount of a diatomic gas is 14.4 J/K. (a) Find the number of moles of the gas. (b) What is the internal energy of the gas at T = 300 K? (c) What is the molar heat capacity of this gas at constant volume? (d) What is the heat capacity of this gas at constant volume? Picture the Problem (a) The number of moles of the gas is related to its heat capacity at constant pressure and its molar heat capacity at constant pressure according to C P = nc' P . For a diatomic gas, the molar heat capacity at constant pressure is c' P = 7 R . (b) The internal energy of a gas depends on its number of 2 degrees of freedom and, for a diatomic gas, is given by Eint = 5 nRT . (c) The 2

molar heat capacity of this gas at constant volume is related to its molar heat capacity at constant pressure according to c' V = c' P R . (d) The heat capacity of this gas at constant volume is the product of the number of moles in the gas and its molar heat capacity at constant volume. (a) The number of moles of the gas is the ratio of its heat capacity at constant pressure to its molar heat capacity at constant pressure: For a diatomic gas, the molar heat capacity is given by:
n= CP c' P

c' P = 7 R = 29.1 2

J mol K

Substitute numerical values and evaluate n:

J K = 0.4948 mol n= J 29.1 mol K 14.4 = 0.495 mol

(b) With 5 degrees of freedom at this temperature:

Eint = 5 nRT 2

Heat and the First Law of Thermodynamics Substitute numerical values and evaluate Eint:
Eint =
5 2

371

(0.4948 mol) 8.314

J (300 K ) = 3.09 kJ mol K

c' V = c' P R

(c) The molar heat capacity of this gas at constant volume is the difference between the molar heat capacity at constant pressure and the gas constant R: Because c' P = 7 R for a diatomic gas: 2 Substitute the numerical value of R to obtain:

c' V = 7 R R = 5 R 2 2

J J c' V = 5 8.314 = 20.79 2 mol K mol K J = 20.8 mol K

C' V = nc' V

(d) The heat capacity of this gas at constant volume is given by: Substitute numerical values and evaluate C' V :

J C' V = (0.4948 mol) 20.79 mol K J = 10.3 K

65 Carbon dioxide (CO2) at a pressure of 1.00 atm and a temperature of 78.5C sublimates directly from a solid to a gaseous state without going through a liquid phase. What is the change in the heat capacity at constant pressure per mole of CO2 when it undergoes sublimation? (Assume that the gas molecules can rotate but do not vibrate.) Is the change in the heat capacity positive or negative during sublimation? The CO2 molecule is pictured in Figure 18-22. Picture the Problem We can find the change in the heat capacity at constant pressure as CO2 undergoes sublimation from the energy per molecule of CO2 in the solid and gaseous states.

Express the change in the heat capacity (at constant pressure) per mole as the CO2 undergoes sublimation:

CP = CP,gas CP,solid

(1)

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Chapter 18

Express Cp,gas in terms of the number of degrees of freedom per molecule:

CP,gas = f ( 1 Nk ) = 5 Nk 2 2 because each molecule has three translational and two rotational degrees of freedom in the gaseous state.
CP,solid = 3Nk 3 atoms = 9 Nk atom

We know, from the Dulong-Petit Law, that the molar specific heat of most solids is 3R = 3Nk. This result is essentially a per-atom result as it was obtained for a monatomic solid with six degrees of freedom. Use this result and the fact CO2 is triatomic to express CP,solid: Substitute in equation (1) to obtain:

C P = 5 Nk 18 Nk = 13 Nk 2 2 2

Quasi-Static Adiabatic Expansion of a Gas

69 A 0.500-mol sample of an ideal monatomic gas at 400 kPa and 300 K, expands quasi-statically until the pressure decreases to 160 kPa. Find the final temperature and volume of the gas, the work done by the gas, and the heat absorbed by the gas if the expansion is (a) isothermal and (b) adiabatic. Picture the Problem We can use the ideal-gas law to find the initial volume of the gas. In Part (a) we can apply the ideal-gas law for a fixed amount of gas to find the final volume and the expression for the work done in an isothermal process. Application of the first law of thermodynamics will allow us to find the heat absorbed by the gas during this process. In Part (b) we can use the relationship between the pressures and volumes for a quasi-static adiabatic process to find the final volume of the gas. We can apply the ideal-gas law to find the final temperature and, as in (a), apply the first law of thermodynamics, this time to find the work done by the gas.

Use the ideal-gas law to express the initial volume of the gas:

Vi =

nRTi Pi

Substitute numerical values and evaluate Vi:

(0.500 mol) 8.314

Vi =

J (300 K ) mol K = 3.118 10 3 m 3 400 kPa Tf = Ti = 300 K

(a) Because the process is isothermal:

Heat and the First Law of Thermodynamics Use the ideal-gas law for a fixed amount of gas with T constant to express Vf: Substitute numerical values and evaluate Vf:
Pi Pf

373

PiV = Pf Vf Vf = Vi

400 kPa Vf = (3.118 L ) 160 kPa = 7.795 L = 7.80 L

Express the work done by the gas during the isothermal expansion: Substitute numerical values and evaluate Wby gas:

Wby gas = nRT ln

Vf Vi

J Wby gas = (0.500 mol) 8.314 mol K 7.795 L (300 K )ln 3.118 L = 1.14 kJ

Noting that the work done by the gas during the process equals the negative of the work done on the gas, apply the first law of thermodynamics to find the heat absorbed by the gas: (b) Using = 5/3 and the relationship between the pressures and volumes for a quasi-static adiabatic process, express Vf: Substitute numerical values and evaluate Vf:

Qin = Eint Won = 0 ( 1.14 kJ ) = 1.14 kJ

P PiVi = Pf Vf Vf = Vi i P f

400 kPa Vf = (3.118 L ) 160 kPa = 5.40 L

35

= 5.403 L

Apply the ideal-gas law to find the final temperature of the gas:

Tf =

Pf Vf nR

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Chapter 18
Tf =

Substitute numerical values and evaluate Tf:

(160 kPa )(5.403 10 3 m 3 ) (0.500 mol) 8.314

J mol K

= 208 K

For an adiabatic process: Apply the first law of thermodynamics to express the work done on the gas during the adiabatic process: Substitute numerical values and evaluate Won:

Qin = 0
Won = Eint Qin = CV T 0 = 3 nRT 2

Won =

3 2

(0.500 mol)(8.314 J/mol K ) (208 K 300 K )

= 574 J Because the work done by the gas equals the negative of the work done on the gas: Wby gas = ( 574 J ) = 574 J

Cyclic Processes
73 A 1.00-mol sample of an ideal diatomic gas is allowed to expand. This expansion is represented by the straight line from 1 to 2 in the PV diagram (Figure 18-23). The gas is then compressed isothermally. This compression is represented by the straight line from 2 to 1 in the PV diagram. Calculate the work per cycle done by the gas. Picture the Problem The total work done as the gas is taken through this cycle is the area bounded by the two processes. Because the process from 12 is linear, we can use the formula for the area of a trapezoid to find the work done during this expansion. We can use Wisothermal process = nRT ln(Vf Vi ) to find the work done

on the gas during the process 21. The net work done during this cycle is then the sum of these two terms. Express the net work done per cycle:

Wnet = Wby the gas + Won the gas = W12 + W21

(1)

Heat and the First Law of Thermodynamics Work is done by the gas during its expansion from 1 to 2 and hence is equal to the negative of the area of the trapezoid defined by this path and the vertical lines at V1 = 11.5 L and V2 = 23 L. Use the formula for the area of a trapezoid to express W12: Work is done on the gas during the isothermal compression from V2 to V1 and hence is equal to the area under the curve representing this process. Use the expression for the work done during an isothermal process to express W21:
W1 2 = Atrap = 1 (23 L 11.5 L ) 2

375

(2.0 atm + 1.0 atm ) = 17.3 L atm

V W21 = nRT ln f V i

Apply the ideal-gas law at point 1 to find the temperature along the isotherm 21:
T=

(2.0 atm )(11.5 L ) PV = = 280 K nR (1.00 mol ) 8.206 10 2 L atm/mol K

Substitute numerical values and evaluate W21:

11.5 L W21 = (1.00 mol) 8.206 10 2 L atm/mol K (280 K )ln 23 L = 15.9 L atm

Substitute in equation (1) and evaluate Wnet:

Wnet = 17.3 L atm + 15.9 L atm = 1.40 L atm = 0.14 kJ 101.325 J L atm

75 At point D in Figure 18-24 the pressure and temperature of 2.00 mol of an ideal monatomic gas are 2.00 atm and 360 K, respectively. The volume of the gas at point B on the PV diagram is three times that at point D and its pressure is twice that at point C. Paths AB and CD represent isothermal processes. The gas is carried through a complete cycle along the path DABCD. Determine the total amount of work done by the gas and the heat absorbed by the gas along each portion of the cycle.

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Chapter 18

Picture the Problem We can find the temperatures, pressures, and volumes at all points for this ideal monatomic gas (3 degrees of freedom) using the ideal-gas law and the work for each process by finding the areas under each curve. We can find the heat exchanged for each process from the heat capacities and the initial and final temperatures for each process.

Express the total work done by the gas per cycle: 1. Use the ideal-gas law to find the volume of the gas at point D:

Wby gas,tot = WDA + WAB + WBC + WCD

VD =

nRTD PD

J (360 K ) mol K = (2.00 atm )101.325 kPa atm = 29.54 L 2. Were given that the volume of the gas at point B is three times that at point D:

(2.00 mol) 8.314

VB = VC = 3VD = 3(29.54 L ) = 88.62 L

Use the ideal-gas law to find the pressure of the gas at point C:

PC =

nRTC = VC

(2.00 mol) 8.206 10 2

88.62 L

L atm (360 K ) mol K

= 0.6667 atm

Were given that the pressure at point B is twice that at point C: 3. Because path DC represents an isothermal process: Use the ideal-gas law to find the temperatures at points B and A:

PB = 2 PC = 2(0.6667 atm ) = 1.333 atm

TD = TC = 360 K

TA = TB =

PBVB nR (1.333 atm )(88.62 L ) = (2.00 mol) 8.206 10 2 L atm mol K = 719.8 K

Heat and the First Law of Thermodynamics Because the temperature at point A is twice that at D and the volumes are the same, we can conclude that: The pressure, volume, and temperature at points A, B, C, and D are summarized in the table to the right.

377

PA = 2 PD = 4.00 atm

Point A B C D

P (atm) 4.00 1.33 0.667 2.00

V (L) 29.5 88.6 88.6 29.5

T (K) 720 720 360 360

4. For the path DA, WDA = 0 and:

QDA = Eint, DA = 3 nRTDA 2 = 3 nR(TA TD ) 2

Substitute numerical values and evaluate QDA:

QD A =
3 2

(2.00 mol) 8.314

J (720 K 360 K ) = 8.979 kJ mol K

For the path AB:

V WAB = QAB = nRTA,B ln B V A

Substitute numerical values and evaluate WAB:

88.62 L J WAB = (2.00 mol) 8.314 (720 K )ln 29.54 L = 13.15 kJ mol K and, because process AB is isothermal, Eint, AB = 0
For the path BC, WBC = 0 , and:

QBC = U BC = C V T = 3 nR(TC TB ) 2

Substitute numerical values and evaluate QBC:

QB C =
3 2

(2.00 mol)(8.314 J/mol K )(360 K 720 K ) = 8.979 kJ

V WCD = nRTC,D ln D V C

For the path CD:

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Chapter 18

Substitute numerical values and evaluate WCD:

29.54 L J WCD = (2.00 mol) 8.314 (360 K )ln 88.62 L = 6.576 kJ mol K Also, because process AB is isothermal, Eint,AB = 0 , and
QCD = WCD = 6.58 kJ

Qin, Won, and Eint are summarized for each of the processes in the table to the right.

Process DA AB BC CD

Qin (kJ)

8.98 13.2
8.98 6.58

Won (kJ) 0 13.2

Eint (kJ) 8.98

0
8.98

0 6.58

Referring to the table, find the total work done by the gas per cycle:
Wby gas, tot = WD A + WA B + WBC + WC D = 0 + 13.2 kJ + 0 6.58 kJ = 6.6 kJ
Remarks: Note that, as it should be, Eint is zero for the complete cycle.

General Problems
79 The PV diagram in Figure 18-25 represents 3.00 mol of an ideal monatomic gas. The gas is initially at point A. The paths AD and BC represent isothermal changes. If the system is brought to point C along the path AEC, find (a) the initial and final temperatures of the gas, (b) the work done by the gas, and (c) the heat absorbed by the gas. Picture the Problem We can use the ideal-gas law to find the temperatures TA and TC. Because the process EDC is isobaric, we can find the area under this line geometrically and then use the 1st law of thermodynamics to find QAEC.

Heat and the First Law of Thermodynamics (a) Using the ideal-gas law, find the temperature at point A:
TA = = PAVA nR

379

(4.0 atm )(4.01 L )

L atm mol K

(3.00 mol) 8.206 10 2

= 65.2 K = 65 K

Using the ideal-gas law, find the temperature at point C:

TC = =

PCVC nR

(1.0 atm )(20.0 L )

L atm mol K

(3.00 mol) 8.206 10 2

= 81.2 K = 81 K

(b) Express the work done by the gas along the path AEC:

WAEC = WAE + WEC = 0 + PEC VEC

= (1.0 atm )(20.0 L 4.01 L ) 101.325 J = 15.99 L atm L atm = 1.62 kJ = 1.6 kJ

(c) Apply the first law of thermodynamics to express QAEC:

QAEC = WAEC + Eint = WAEC + CV T = WAEC + 3 nRT 2 = WAEC + 3 nR(TC TA ) 2

Substitute numerical values and evaluate QAEC:

QAEC = 1.62 kJ + 3 (3.00 mol)(8.314 J/mol K )(81.2 K 65.2 K ) = 2.2 kJ 2
Remarks The difference between WAEC and QAEC is the change in the internal energy Eint,AEC during this process.

As part of a laboratory experiment, you test the calorie content of 83 various foods. Assume that when you eat these foods, 100% of the energy released by the foods is absorbed by your body. Suppose you burn a 2.50-g potato chip, and the resulting flame warms a small aluminum can of water. After burning the potato chip, you measure its mass to be 2.20 g. The mass of the can is 25.0 g, and the volume of water contained in the can is 15.0 ml. If the temperature increase in the water is 12.5C, how many kilocalories

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Chapter 18

(1 kcal = 1 dietary calorie) per 150-g serving of these potato chips would you estimate there are? Assume the can of water captures 50.0 percent of the heat released during the burning of the potato chip. Note: Although the joule is the SI unit of choice in most thermodynamic situations, the food industry in the United States currently expresses the energy released during metabolism in terms of the dietary calorie, which is our kilocalorie.
Picture the Problem The ratio of the energy in a 150-g serving to the energy in 0.30 g of potato chip is the same as the ratio of the masses of the serving and the amount of the chip burned while heating the aluminum can and the water in it.

The ratio of the energy in a 150-g serving to the energy in 0.30 g of potato chip is the same as the ratio of the masses of the serving and the amount of the chip burned while heating the aluminum can and the water in it:
Letting f represent the fraction of the heat captured by the can of water, express the energy transferred to the aluminum can and the water in it during the burning of the potato chip: Substituting for Q0.30 g yields and solving for Q150-g serving yields:

Q150-g serving Q0.30 g

150 g = 500 0.30 g

or Q150 g serving = 500Q0.30 g

fQ0.30 g = QAl + QH 2 O = mAl cAl T + mH 2 O cH 2 O T = mAl cAl + mH 2 O cH 2 O T

where T is the common temperature change of the aluminum cup and the water it contains.

Q150-g serving =

500 mAl cAl + mH 2O cH 2 O T

f

Substitute numerical values and evaluate Q150-g serving :

kJ kJ + (0.0150 kg ) 4.184 (12.5 C) 500 (0.0250 kg ) 0.900 kg K kg K = 0.500 1 cal = 1.07 10 6 J = 256 10 3 cal 256 kcal 4.184 J

Q150 -g serving

A thermally insulated system consists of 1.00 mol of a diatomic gas at 89 100 K and 2.00 mol of a solid at 200 K that are separated by a rigid insulating

Heat and the First Law of Thermodynamics

381

wall. Find the equilibrium temperature of the system after the insulating wall is removed, assuming that the gas obeys the ideal-gas law and that the solid obeys the DulongPetit law.
Picture the Problem We can use conservation of energy to relate the equilibrium temperature to the heat capacities of the gas and the solid. We can apply the Dulong-Petit law to find the heat capacity of the solid at constant volume and use the fact that the gas is diatomic to find its heat capacity at constant volume.

Apply conservation of energy to this process:

Q = Qgas + Qsolid = 0

Use Q = C V T to substitute for Qgas and Qsolid:

C V,gas (Tequil 100 K ) + C V,solid (Tequil 200 K ) = 0

Solving for Tequil yields:
Tequil =

(100 K )(CV,gas ) + (200 K )(CV,solid )

C V,gas + C V,solid

Using the Dulong-Petit law, determine the heat capacity of the solid at constant volume: The heat capacity of the gas at constant volume is given by:

CV,solid = 3nsolid R

C V,gas = 5 ngas R 2

Substitute for CV,solid and CV,gas and simplify to obtain: Tequil =

(100 K )(5 ngas R ) + (200 K )(3nsolid R ) (100 K )(5 ngas ) + (200 K )(3nsolid ) 2 2
5 2

ngas R + 3nsolid R

5 2

ngas + 3nsolid

Substitute numerical values for ngas and nsolid and evaluate Tequil:
Tequil =

(100 K )( 5 )(1.00 mol) + (200 K )(3)(2.00 mol) 2 = 5 ( ) ( ) 2 1.00 mol + 3 2.00 mol

171 K

95 (a) Use the results of Problem 94 to show that in the limit that T >> TE , the Einstein model gives the same expression for specific heat that the DulongPetit law does. (b) For diamond, TE is approximately 1060 K. Integrate numerically dEint = cv dT to find the increase in the internal energy if 1.00 mol of diamond is heated from 300 to 600 K.

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Chapter 18

Picture the Problem (a) We can rewrite our expression for c'V by dividing its

numerator and denominator by eTE T and then using the power series for ex to show that, for T > TE, c'V 3R . In Part (b), we can use the result of Problem 94 to obtain values for c'V every 100 K between 300 K and 600 K and use this data to find U numerically. (a) From Problem 94 we have:

eTE T TE c' V = 3R T eTE T 1

Divide the numerator and denominator by eTE T to obtain:

T c' V = 3R E 2TE T e T = 3R E TE T e
2

1 2eTE eTE T

+1

1 2 + e TE

Express the exponential terms in their power series to obtain:

e
TE T

2+e

TE T

T T 1T 1T = 1 + E + E + ... 2 + 1 E + E + ... T 2 T T 2 T T E for T >> TE T

2

Substitute for e TE obtain:

2 + e TE

to

1 T c' V 3R E = 3R 2 T TE T

(b) Use the result of Problem 94 to verify the following table: T cV (K) 300 400 500 600 (J/molK) 9.65 14.33 17.38 19.35

Heat and the First Law of Thermodynamics

383

The following graph of specific heat as a function of temperature was plotted using a spreadsheet program:
21 19 17

C V (J/mol-K)

15 13 11 9 7 5 300

350

400

450

500

550

600

T (K)

Integrate numerically, using the formula for the area of a trapezoid, to obtain: U =
1 2

(1.00 mol)(100 K )(9.65 + 14.33)

J mol K J mol K J mol K

+ 1 (1.00 mol)(100 K )(14.33 + 17.38) 2

+ 1 (1.00 mol)(100 K )(17.38 + 19.35) 2 = 4.62 kJ

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Chapter 18