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Heat and Thermodynamics

M. W. Zemansky, Richard H. Dittman

Chapter 17

Heterogeneous Systems - all with Video Answers

Educators


Chapter Questions

02:12

Problem 1

All the lettered points in Fig. P17-1 lie in one plane. The line $C D$ separates the plane into two regions: on the left, a wave has the speed $w$; and on the right, the speed $w^{\prime}$. Show by the method of Lagrangian multipliers that the time for the wave to travel the path $A P B$ is a minimum when $w / w^{\prime}=\sin \phi / \sin \phi^{\prime}$.

RZ
Rubeena Zulfiqar
Numerade Educator
15:00

Problem 2

A hot metal of mass $m$, specific heat $c_{P}$, and temperature $T_{i}$ is immersed in a cooler liquid of mass $m^{\prime}$, specific heat $c_{P}^{\prime}$, and temperature $T_{i}^{\prime}$. The entire system is thermally insulated. If the final temperature of the metal is $T_{f}$ and that of the liquid is $T_{f}^{\prime}$, then show by the method of Lagrangian multipliers that the condition for the entropy change of the universe to be a maximum is that $T_{f}=T_{f}^{\prime}$.

Ravindra Yadav
Ravindra Yadav
Numerade Educator
02:20

Problem 3

Consider a homogeneous mixture of four ideal gases capable of undergoing the reaction
$$
v_{1} B_{1}+v_{2} B_{2} \rightleftharpoons v_{3} B_{3}+v_{4} B_{4}
$$
How many components are there if one starts with:
(a) Arbitrary amounts of $B_{1}$ and $B_{2}$ only.
(b) Arbitrary amounts of all four gases.
(c) $v_{1}$ moles of $B_{1}$ and $v_{2}$ moles of $B_{2}$ only.

Ajay Singhal
Ajay Singhal
Numerade Educator
08:06

Problem 4

Consider a system composed of a solid phase of calcium carbonate $\left(\mathrm{CaCO}_{3}\right) ;$ a solid phase of calcium oxide $(\mathrm{CaO}) ;$ and a gaseous phase consisting of a mixture of $\mathrm{CO}_{2}$, $\mathrm{CaCo}_{3}$ vapor, and $\mathrm{CaO}$ vapor, all three constituents being present initially in arbitrary amounts. These are the substances that are present in a limekiln, where the reaction

Amanda Hyde
Amanda Hyde
Numerade Educator
08:47

Problem 5

Solid ammonium bydrosulphide $\left(\mathrm{NH}_{4} \mathrm{HS}\right)$ is mixed with arbitrary amounts of gaseous $\mathrm{NH}_{3}$ and $\mathrm{H}_{2} \mathrm{~S}$, forming a three-constituent system of two phases, undergoing the reaction
$$
\mathrm{NH}_{4} \mathrm{HS} \rightleftharpoons \mathrm{NH}_{3}+\mathrm{H}_{2} \mathrm{~S}
$$
(a) How many components are there, and what is the variance?
(b) Assuming that the gaseous phase is a mixture of ideal gases, show that
$$
\frac{P \mathrm{NH}_{1} P \mathrm{H}_{4} \mathrm{~s}}{P \mathrm{NH}_{4} \mathrm{HS}}=K
$$
(c) If solid $\mathrm{NH}_{4} \mathrm{HS}$ is placed in an evacuated chamber, how many components are there, and what is the variance?

Kevin Zaborsky
Kevin Zaborsky
Numerade Educator
01:09

Problem 6

How many components are there in a system composed of arbitrary amounts of water, sodium chloride, and barium chloride?

Ronald Prasad
Ronald Prasad
Numerade Educator
00:55

Problem 7

At high temperature, the following reactions take place:
$$
\mathrm{C}+\mathrm{CO}_{2}=2 \mathrm{CO}
$$
and
$$
\mathrm{CO}_{2}+\mathrm{H}_{2}=\mathrm{CO}+\mathrm{H}_{2} \mathrm{O}
$$
How many components are there if we start with:
(a) Arbitrary amounts of $\mathrm{C}, \mathrm{CO}_{2}$, and $\mathrm{H}_{2}$ ?
(b) Arbitrary amounts of $\mathrm{C}, \mathrm{CO}_{2}, \mathrm{H}_{2}, \mathrm{CO}$, and $\mathrm{H}_{2} \mathrm{O} ?$

Alkendra Singh
Alkendra Singh
Numerade Educator
01:39

Problem 8

Consider a system consisting of a pure liquid phase in equilibrium with a gaseous phase, composed of a mixture of the vapor of the liquid and an inert gas that is insoluble in the liquid. Suppose that the inert gas (sometimes called the foreign gas) can flow into or out of the gaseous phase, so that the total pressure can be varied at will.
(a) How many components are there, and what is the variance?
(b) Assuming the gaseous phase to be a mixture of ideal gases, show that
$$
g^{\prime \prime}=R T(\phi+\ln p)
$$
where $g^{\prime \prime}$ is the molar Gibbs function of the liquid, and $\phi$ and $p$ refer to the vapor.
(c) Suppose that a little more foreign gas is added, thus increasing the pressure from $P$ to $P+d P$, at constant temperature. Show that
$$
v^{\prime \prime} d P=R T \frac{d p}{P}
$$
where $\nu^{\prime \prime}$ is the molar volume of the liquid, which is practically constant.
(d) Integrating at constant temperature from an initial state, where there is no foreign gas, to a final state, where the total pressure is $P$ and the partial vapor pressure is $p$, show that
$$
\ln \frac{P}{P_{0}}=\frac{v^{\prime \prime}}{R T}\left(P-P_{0}\right) \quad \text { (Gibbs' equation), }
$$
where $P_{0}$ is the vapor pressure when no foreign gas is present.
(e) In the case of water at $0^{\circ} \mathrm{C}$, at which $P_{0}=4.58 \mathrm{~mm} \mathrm{Hg}$, show that, when there is sufficient air above the water to make the total pressure equal to $10 \mathrm{~atm}$, $p=4.62 \mathrm{~mm} \mathrm{Hg}$.

Manik Pulyani
Manik Pulyani
Numerade Educator
02:41

Problem 9

The Gibbs function $G$ of a liquid phase consisting of a solvent and very small amounts of several solutes is
$$
G=\mu_{0} n_{0}+\mu_{1} n_{1}+\mu_{2} n_{2}+\cdots,
$$
where the subscript zero refers to the solvent, and
$$
\mu_{j}=g_{j}+R T \ln x_{j}
$$
(a) Using the relation $V=(\partial G / \partial P)_{T}$, show that
$$
\boldsymbol{V}=\sum n_{j} v_{i}
$$
(b) Using the relation $H=G-T(\partial G / \partial T)_{P}$, show that
$$
H=\sum n_{j} h_{j}
$$
which means that there is no heat of dilution.

Robert Zaballa
Robert Zaballa
Numerade Educator
04:31

Problem 10

A very small amount of sugar is dissolved in water, and the solution is in equilibrium with pure water vapor.
(a) Show that the equation of phase equilibrium is
$$
g^{\prime \prime \prime}=g^{\prime \prime}+R T \ln (1-x)
$$
where $g^{\prime \prime \prime}$ is the molar Gibbs function of water vapor, $g^{n}$ is the molar Gibbs function of pure liquid water, and $x$ is the mole fraction of the sugar in solution.
(b) For an infinitesimal change in $x$ at constant temperature, show that
$$
\left(v^{m}-v^{\prime \prime}\right) d P=R T d \ln (1-x)
$$
(c) Assuming the vapor to behave like an ideal gas and regarding $v^{\prime \prime}$ as constant, integrate the preceding equation at constant temperature from an initial state $x=0, P=P_{0}$, to a final state $x=x, P=P_{x}$, and derive
$$
\ln \frac{P_{x}}{P_{0}}=\ln (1-x)+\frac{\nu^{N}}{R T}\left(P_{x}-P_{0}\right)
$$
where $P_{0}$ is the vapor pressure of the pure liquid and $P_{x}$ is the vapor pressure of the dilute solution.
(d) Justify neglecting the last term on the right, and show that
or
$$
\begin{aligned}
&P_{x}=P_{0}(1-x) \quad \text { (Raoult's law), } \\
&\frac{P_{0}-P_{x}}{P_{0}}=x
\end{aligned}
$$

Lottie Adams
Lottie Adams
Numerade Educator
04:31

Problem 11

Consider the system of Prob. $17.10$, and let $x$ stand for the mole fraction of the sugar.
(a) For an infinitesimal change in $x$ at constant pressure, show that
$$
-s^{\prime \prime \prime} d T=-s^{\prime \prime} d T+R \ln (1-x) d T+R T d \ln (1-x)
$$
(b) Substituting for $R \ln (1-x)$ the value obtained from the equation of phase equilibrium, show that the equation in part $(a)$ reduces to
$$
0=\frac{h^{m \prime \prime}-h^{\prime \prime}}{T} d T+R T d \ln (1-x)
$$
(c) Taking into account that $x<1$ and calling $h^{\prime \prime \prime}-h^{\prime \prime}$ the latent heat of vaporization $l_{y}$, show that the elevation of the boiling point is
$$
\Delta T=\frac{R T^{2}}{l_{y}} x
$$

Lottie Adams
Lottie Adams
Numerade Educator
04:09

Problem 12

A very small amount of sugar is dissolved in water, and the solution is in equilibrium with pure ice. The equation of phase equilibrium is
$$
g^{\prime}=g^{\prime \prime}+R T \ln (1-x)
$$
where $g^{\prime}$ is the molar Gibbs function of pure ice, $g^{\prime \prime}$ is the molar Gibbs function of pure water, and $x$ is the mole fraction of sugar in solution.
(a) For an infinitesimal change in $x$ at constant pressure, show that
$$
-s^{\prime} d T=-s^{\prime \prime} d T+R \ln (1-x) d T+R T d \ln (1-x)
$$
(b) Substituting for $R \ln (1-x)$ the value obtained from the equation of phase equilibrium, show that the equation in part (a) reduces to
$$
\frac{h^{\prime \prime}-h^{\prime}}{T} d T=R T d \ln (1-x)
$$
(c) Taking into account that $x \ll 1$ and calling $h^{\prime \prime}-h^{\prime}$ the latent heat of fusion $l_{F}$, show that the depression of the freezing point is
$$
\Delta T=-\frac{R T^{2}}{l_{F}} x
$$

Natalie Almond
Natalie Almond
Numerade Educator
01:46

Problem 13

In the osmotic pressure apparatus depicted in Fig. $P 17-2$, let the pressure of the pure solvent be $P_{0}$ and that of the dilute solution be $P$, the temperature being $T$ throughout the system. The molar Gibbs function of the pure solvent is $g^{\prime \prime}$.
(a) Show that, at equilibrium,
$$
g^{n}\left(T, P_{0}\right)=g^{n}(T, P)+R T \ln (1-x)
$$
where $x$ is the mole-fraction of the solute.
(b) For an infinitesimal change of $x$ at constant $T$; show that
$$
0=v^{\prime \prime} d P+R T d \ln (1-x)
$$

Manik Pulyani
Manik Pulyani
Numerade Educator