<Chap 18.

Heat, Work, and the First Law of Thermodynamics>

18.12, 18.16, 18.24, 18.53, 18.56, 18.74

18.12

In a closed but uninsulated container, 500 g of water are shaken violently until the temperature rises
by 3.0°C. The mechanical work done in the stirring process is 9.0 kJ.

(a) How much heat is transferred to the surroundings during the shaking?
(b) How much mechanical energy would have been required if the container had been perfectly
insulated?
(c.f. specific heat capacity of water is 4.184 J⋅g−1⋅K −1)

Solution

(a)
Mechanical work done on the water is

𝑊𝑊 = +9.0kJ (𝟏𝟏𝟏𝟏𝟏𝟏𝟏𝟏)

Δ𝐸𝐸𝑖𝑖𝑖𝑖𝑖𝑖 = mc∆T = (500g)(4.184J/g ∙ K)(3.0K) = 6276J = 6.276kJ (𝟏𝟏𝟏𝟏𝟏𝟏𝟏𝟏)

Applying the First Law of Thermodynamics:

Δ𝐸𝐸𝑖𝑖𝑖𝑖𝑖𝑖 = 𝑄𝑄 + 𝑊𝑊 (𝟏𝟏𝟏𝟏𝟏𝟏𝟏𝟏)

𝑄𝑄 = Δ𝐸𝐸𝑖𝑖𝑖𝑖𝑖𝑖 − W = 6.276𝑘𝑘𝑘𝑘 − 9.0𝑘𝑘𝑘𝑘 = −2.724kJ ≈ −2.7kJ (𝟏𝟏𝟏𝟏𝟏𝟏𝟏𝟏)

Negative 𝑄𝑄 means heat leaves the system. Answer is 2.7𝑘𝑘𝑘𝑘.

(b)
The container had been perfectly insulated:

Q=0 (𝟏𝟏𝟏𝟏𝟏𝟏𝟏𝟏)

W = Δ𝐸𝐸𝑖𝑖𝑖𝑖𝑖𝑖 = mc∆T = (500g)(4.184J/g ∙ K)(3.0K) = 6.276kJ ≈ 6.3kJ (𝟏𝟏𝟏𝟏𝟏𝟏𝟏𝟏)

18.16

An ideal gas expands from the state (𝑝𝑝1 , 𝑉𝑉1 ) to the state (𝑝𝑝2 , 𝑉𝑉2 ), where 𝑝𝑝2 = 2𝑝𝑝1 and 𝑉𝑉2 = 2𝑉𝑉1 . The
expansion proceeds along the diagonal path 𝐴𝐴𝐴𝐴 in Fig. 18.19. Find an expression for the work done
by the gas during this process.

Figure 18.19

Solution

Total work done during the process is:

𝑉𝑉2
𝑊𝑊 = � 𝑝𝑝𝑝𝑝𝑝𝑝 (𝟏𝟏𝟏𝟏 𝐩𝐩𝐩𝐩)
𝑉𝑉1

We can see that we have straight slanted line. We can define the line using point-slope form:
𝑦𝑦2 − 𝑦𝑦1 𝑝𝑝2 − 𝑝𝑝1 𝑝𝑝1
𝑘𝑘 = = =
𝑥𝑥2 − 𝑥𝑥1 𝑉𝑉2 − 𝑉𝑉1 𝑉𝑉1

The equation defining the path 𝐴𝐴𝐴𝐴 is therefore:

𝑝𝑝 − 𝑝𝑝1 = 𝑘𝑘(𝑉𝑉 − 𝑉𝑉1 )

𝑝𝑝1 (𝑉𝑉 − 𝑉𝑉1 )

𝑝𝑝 = 𝑝𝑝1 + (𝟐𝟐𝟐𝟐 𝐩𝐩𝐩𝐩)
𝑉𝑉1

Returning the definition of pressure into the first equation, we can determine the total work done:
𝑉𝑉2 2𝑉𝑉1 2𝑉𝑉1
𝑝𝑝1 (𝑉𝑉 − 𝑉𝑉1 )𝑑𝑑𝑑𝑑
𝑊𝑊 = � 𝑝𝑝𝑝𝑝𝑝𝑝 = � 𝑝𝑝1 𝑑𝑑𝑑𝑑 + �
𝑉𝑉1 𝑉𝑉1 𝑉𝑉1 𝑉𝑉1
2𝑉𝑉1
𝑝𝑝1 2𝑉𝑉1 𝑝𝑝1 2𝑉𝑉1
=� 𝑝𝑝1 𝑑𝑑𝑑𝑑 + � 𝑉𝑉𝑉𝑉𝑉𝑉 − � 𝑉𝑉1 𝑑𝑑𝑑𝑑
𝑉𝑉1 𝑉𝑉1 𝑉𝑉1 𝑉𝑉1 𝑉𝑉1

𝑝𝑝1 (2𝑉𝑉1 )2 − 𝑉𝑉12 𝑝𝑝1 𝑉𝑉1

= 𝑝𝑝1 (2𝑉𝑉1 − 𝑉𝑉1 ) + � �− (2𝑉𝑉1 − 𝑉𝑉1 )
𝑉𝑉1 2 𝑉𝑉1

3𝑉𝑉12 𝑝𝑝1
= 𝑝𝑝1 𝑉𝑉1 + − 𝑝𝑝1 𝑉𝑉1
2𝑉𝑉1
3𝑝𝑝1 𝑉𝑉1
= (𝟑𝟑𝟑𝟑 𝐩𝐩𝐩𝐩)
2
18.24

A gas mixture contains 2.5 mol of O2 and 3.0 mol of Ar. What are this mixture’s molar specific heats
𝐶𝐶𝑉𝑉 and 𝐶𝐶𝑝𝑝 at constant volume and constant pressure?

Solution

We have a mixture of oxygen and argon with the amount of oxygen 𝑛𝑛O2 = 2.5 mol and of argon
𝑛𝑛Ar = 3.0 mol. Volume specific heat is a part of equation determining internal energy:

𝐸𝐸int = 𝑛𝑛𝐶𝐶𝑉𝑉 ∆𝑇𝑇

5𝑘𝑘𝐵𝐵 𝑇𝑇 3𝑘𝑘𝐵𝐵 𝑇𝑇
Diatomic oxygen has 𝐸𝐸int = energy per molecule, while single atomic 𝐸𝐸𝑖𝑖𝑖𝑖𝑖𝑖 = energy
2 2
per molecule. (𝟏𝟏𝟏𝟏 𝐩𝐩𝐩𝐩)

Internal energy of 2.5 moles of oxygen is:

5𝑘𝑘𝐵𝐵 𝑇𝑇 5𝑛𝑛𝑛𝑛𝑛𝑛
𝐸𝐸int(O2) = 𝑛𝑛𝑁𝑁𝑎𝑎 = = 2.5 · 2.5 · 𝑅𝑅𝑅𝑅 = 6.25𝑅𝑅𝑅𝑅 (𝟓𝟓 𝐩𝐩𝐩𝐩)
2 2
Internal energy of 3.0 moles of argon is:
3𝑘𝑘𝐵𝐵 𝑇𝑇 3𝑛𝑛𝑛𝑛𝑛𝑛
𝐸𝐸int(Ar) = 𝑛𝑛𝑁𝑁𝑎𝑎 = = 1.5 · 3.0 · 𝑅𝑅𝑅𝑅 = 4.5𝑅𝑅𝑅𝑅 (𝟓𝟓 𝐩𝐩𝐩𝐩)
2 2
Total internal energy is therefore:

𝐸𝐸int(total) = 𝐸𝐸int(O2) + 𝐸𝐸int(Ar) = 6.25𝑅𝑅𝑅𝑅 + 4.5𝑅𝑅𝑅𝑅 = 10.75𝑅𝑅𝑅𝑅 (𝟏𝟏𝟏𝟏 𝐩𝐩𝐩𝐩)

Deriving volume specific heat from the equation for internal energy will give us:
𝐸𝐸int
𝐸𝐸int = 𝑛𝑛𝐶𝐶𝑉𝑉 ∆𝑇𝑇 ⇒ 𝐶𝐶𝑉𝑉 = (𝟏𝟏𝟏𝟏 𝐩𝐩t)
𝑛𝑛∆𝑇𝑇
Inserting the total Internal energy will give us mixture’s volume specific heat:
𝐸𝐸int 10.75𝑅𝑅𝑅𝑅
𝐶𝐶𝑉𝑉 = = = 1.95𝑅𝑅 (𝟏𝟏𝟏𝟏 𝐩𝐩𝐩𝐩)
𝑛𝑛∆𝑇𝑇 5.5 mol · T
Pressure specific heat is simply addition of volume specific heat and 𝑅𝑅, meaning its value in this
case will be:

𝐶𝐶𝑝𝑝 = 𝐶𝐶𝑉𝑉 + 𝑅𝑅 = 1.95𝑅𝑅 + 𝑅𝑅 = 2.95𝑅𝑅 (𝟏𝟏𝟏𝟏 𝐩𝐩𝐩𝐩)

18.53

An ideal gas with γ = 1.28 starts at point A in Fig. 18.21, where its
volume and pressure are 1.00 m3 and 250 kPa, respectively. It
undergoes an adiabatic expansion that triples its volume, ending at B.
It's then heated at constant volume to C and compressed isothermally
back to A.

(a) Find the pressure at B. (15pt)

(b) Find the pressure at C. (15pt)
(c) Find the net work done on the gas. (30pt)

Solution

The problem involves a cyclic process with three separate stages:

adiabatic, isochoric, and isothermal.

(a)
AB is adiabatic process:
𝛄𝛄 𝜸𝜸
𝐩𝐩𝐀𝐀 𝐕𝐕𝐀𝐀 = 𝒑𝒑𝑩𝑩 𝑽𝑽𝑩𝑩 (𝟓𝟓𝟓𝟓𝟓𝟓)

𝑽𝑽𝑨𝑨 𝛄𝛄 𝟏𝟏 𝟏𝟏.𝟔𝟔𝟔𝟔
𝐩𝐩𝐁𝐁 = 𝒑𝒑𝑨𝑨 � � = (𝟐𝟐𝟐𝟐𝟐𝟐𝟐𝟐𝟐𝟐𝟐𝟐) � � = 𝟑𝟑𝟑𝟑. 𝟗𝟗 𝒌𝒌𝒌𝒌𝒌𝒌 ≈ 𝟒𝟒𝟒𝟒 𝒌𝒌𝒌𝒌𝒌𝒌 (𝟏𝟏𝟏𝟏𝟏𝟏𝟏𝟏)
𝑽𝑽𝑩𝑩 𝟑𝟑

(b)
A and C is same temperature. Using the ideal gas law:
𝑽𝑽𝑨𝑨 𝟐𝟐𝟐𝟐𝟐𝟐𝟐𝟐𝟐𝟐𝟐𝟐
𝒑𝒑𝑪𝑪 = 𝒑𝒑𝑨𝑨 � �= = 𝟖𝟖𝟖𝟖. 𝟑𝟑 𝒌𝒌𝒌𝒌𝒌𝒌 (𝟏𝟏𝟏𝟏𝟏𝟏𝟏𝟏)
𝑽𝑽𝑪𝑪 𝟑𝟑

(c)
𝐖𝐖𝐀𝐀𝐀𝐀𝐀𝐀𝐀𝐀 = 𝐖𝐖𝐀𝐀𝐀𝐀 + 𝐖𝐖𝐁𝐁𝐁𝐁 + 𝐖𝐖𝐂𝐂𝐂𝐂

AB: The adiabatic process.

Using (equation 18.12) (or integrating adiabatic process)

𝐩𝐩𝐁𝐁 𝐕𝐕𝐁𝐁 − 𝐩𝐩𝐀𝐀 𝐕𝐕𝐀𝐀 (𝟑𝟑𝟑𝟑. 𝟗𝟗𝟗𝟗𝟗𝟗𝟗𝟗)(𝟑𝟑. 𝟎𝟎𝟎𝟎𝐦𝐦𝟑𝟑 ) − (𝟐𝟐𝟐𝟐𝟐𝟐𝟐𝟐𝟐𝟐𝟐𝟐)(𝟏𝟏. 𝟎𝟎𝟎𝟎𝐦𝐦𝟑𝟑 )

𝑾𝑾𝑨𝑨𝑨𝑨 = = = −𝟏𝟏𝟏𝟏𝟏𝟏. 𝟓𝟓 𝒌𝒌𝒌𝒌 (𝟏𝟏𝟏𝟏𝟏𝟏𝟏𝟏)
𝛄𝛄 − 𝟏𝟏 𝟎𝟎. 𝟔𝟔𝟔𝟔

BC: The isochoric process. ∴ 𝑾𝑾𝑩𝑩𝑩𝑩 = 𝟎𝟎 (𝟓𝟓𝟓𝟓𝟓𝟓)

CA: The isothermal process.

𝑽𝑽𝑨𝑨 𝑽𝑽𝑨𝑨 𝟏𝟏
𝐖𝐖𝐂𝐂𝐂𝐂 = −𝒏𝒏𝒏𝒏𝑻𝑻𝑨𝑨 𝒍𝒍𝒏𝒏 � � = −𝑷𝑷𝑨𝑨 𝑽𝑽𝑨𝑨 𝒍𝒍𝒍𝒍 � � = −(𝟐𝟐𝟐𝟐𝟐𝟐𝟐𝟐𝟐𝟐)𝒍𝒍𝒍𝒍 � � = 𝟐𝟐𝟐𝟐𝟐𝟐. 𝟔𝟔𝟔𝟔𝟔𝟔 (𝟏𝟏𝟏𝟏𝟏𝟏𝟏𝟏)
𝑽𝑽𝑪𝑪 𝑽𝑽𝑪𝑪 𝟑𝟑

∴ 𝐖𝐖𝐀𝐀𝐀𝐀𝐀𝐀𝐀𝐀 = 𝐖𝐖𝐀𝐀𝐀𝐀 + 𝐖𝐖𝐁𝐁𝐁𝐁 + 𝐖𝐖𝐂𝐂𝐂𝐂 = −𝟏𝟏𝟏𝟏𝟏𝟏. 𝟓𝟓 𝒌𝒌𝒌𝒌 + 𝟎𝟎 + 𝟐𝟐𝟐𝟐𝟐𝟐. 𝟔𝟔 𝒌𝒌𝒌𝒌 = 𝟖𝟖𝟖𝟖. 𝟏𝟏 𝒌𝒌𝒌𝒌 ≈ 𝟖𝟖𝟖𝟖 𝐤𝐤𝐤𝐤 (𝟓𝟓𝟓𝟓𝟓𝟓)
18.56

Show that the relation between pressure and temperature in an adiabatic process is 𝑝𝑝1−𝛾𝛾 𝑇𝑇 𝛾𝛾 = const.

Solution

If we take the changes for temperature and volume as infinitesimally small, combining equations
first law of thermodynamics and internal energy:

𝐶𝐶𝑉𝑉 𝑑𝑑𝑑𝑑 = −𝑝𝑝𝑝𝑝𝑝𝑝 (𝟓𝟓 𝐩𝐩𝐩𝐩)

Deriving the pressure from equation (1) will give us: (𝑛𝑛 = 1)
𝑅𝑅𝑅𝑅
𝑝𝑝 = (𝟓𝟓 𝐩𝐩𝐩𝐩)
𝑉𝑉
This makes the following equation:
𝐶𝐶𝑉𝑉 𝑑𝑑𝑑𝑑 𝑅𝑅𝑅𝑅𝑅𝑅
=− (𝟓𝟓 𝐩𝐩𝐩𝐩)
𝑇𝑇 𝑉𝑉
We will now integrate the above expression:
𝑇𝑇2 𝑉𝑉2
𝑑𝑑𝑑𝑑 𝑑𝑑𝑑𝑑 𝑇𝑇2 𝑉𝑉2
𝐶𝐶𝑉𝑉 � = −𝑅𝑅 � → 𝐶𝐶𝑉𝑉 ln � � = −𝑅𝑅 ln � � (𝟓𝟓 𝐩𝐩𝐩𝐩)
𝑇𝑇1 𝑇𝑇 𝑉𝑉1 𝑉𝑉 𝑇𝑇1 𝑉𝑉1

Relation between pressure and volume specific heat is 𝐶𝐶𝑝𝑝 = 𝐶𝐶𝑉𝑉 + 𝑅𝑅. (𝟓𝟓 𝐩𝐩𝐩𝐩)

Inserting that into the above equation:

𝑇𝑇2 𝐶𝐶𝑝𝑝 𝑉𝑉2
ln � � = − � − 1� ln � � (𝟏𝟏𝟏𝟏 𝐩𝐩𝐩𝐩)
𝑇𝑇1 𝐶𝐶𝑉𝑉 𝑉𝑉1
𝐶𝐶𝑝𝑝
We know that 𝛾𝛾 = : (10 pt)
𝐶𝐶𝑉𝑉

𝑇𝑇2 𝑉𝑉2 𝑇𝑇2 𝑉𝑉1 𝛾𝛾−1 𝛾𝛾−1 𝛾𝛾−1

ln � � = −(𝛾𝛾 − 1) ln � � → =� � → 𝑇𝑇1 𝑉𝑉1 = 𝑇𝑇2 𝑉𝑉2 (𝟏𝟏𝟏𝟏 𝐩𝐩𝐩𝐩)
𝑇𝑇1 𝑉𝑉1 𝑇𝑇1 𝑉𝑉2

Using the ideal gas law again, we can derive between the pressure and volume:
𝛾𝛾−1 𝛾𝛾−1
𝑝𝑝1 𝑉𝑉1 ∙ 𝑉𝑉1 𝑝𝑝2 𝑉𝑉2 ∙ 𝑉𝑉2
=
𝑅𝑅 𝑅𝑅
𝛾𝛾 𝛾𝛾
𝑝𝑝1 𝑉𝑉1 = 𝑝𝑝2 𝑉𝑉2

𝑅𝑅𝑇𝑇1 𝛾𝛾 𝑅𝑅𝑇𝑇2 𝛾𝛾
𝑝𝑝1 � � = 𝑝𝑝2 � �
𝑝𝑝1 𝑝𝑝2
1−𝛾𝛾 𝛾𝛾 1−𝛾𝛾 𝛾𝛾
𝑝𝑝1 𝑇𝑇1 = 𝑝𝑝2 𝑇𝑇2

We can assume that 𝑝𝑝1−𝛾𝛾 𝑇𝑇 𝛾𝛾 = const. (𝟏𝟏𝟏𝟏 𝐩𝐩𝐩𝐩)

18.74

A real gas is more accurately described using the van der Waals equation:

[p + a(n/V)2 ](V − nb) = nRT

where a and b are constants.

V2
Find an expression, corresponding to Equation 18.4 (Q = −W = nRT ln ), for the work done by a van
V1
der Waals gas undergoing an isothermal expansion from V1 to V2.

Solution

Pressure for van der Waals equation:

𝑛𝑛𝑛𝑛𝑛𝑛 𝑛𝑛 2
p= − 𝑎𝑎 � � (𝟏𝟏𝟏𝟏𝟏𝟏𝟏𝟏)
𝑉𝑉 − 𝑛𝑛𝑛𝑛 𝑉𝑉
Performing the integration:
𝑉𝑉2 𝑉𝑉2
𝑛𝑛𝑛𝑛𝑛𝑛 𝑎𝑎𝑛𝑛2
W = − � 𝑝𝑝𝑝𝑝𝑝𝑝 = − � − 2 𝑑𝑑𝑑𝑑 (𝟐𝟐𝟐𝟐𝟐𝟐𝟐𝟐)
𝑉𝑉1 𝑉𝑉1 𝑉𝑉 − 𝑛𝑛𝑛𝑛 𝑉𝑉
𝑉𝑉
𝑎𝑎𝑛𝑛2 2
W = − �𝑛𝑛𝑛𝑛𝑛𝑛 𝑙𝑙𝑙𝑙(𝑉𝑉 − 𝑛𝑛𝑛𝑛) + �
𝑉𝑉 𝑉𝑉
1
V1 − nb 1 1
W = nRT ln � � + an2 � − � (𝟑𝟑𝟑𝟑𝟑𝟑𝟑𝟑)
V2 − nb V1 V2