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Introduction to Chemical Engineering Thermodynamics

J. M. Smith, Hendrick C Van Ness, Michael Abbott, Hendrick Van Ness

Chapter 13

CHEMICAL-REACTION EQUILIBRIA - all with Video Answers

Educators


Chapter Questions

02:22

Problem 1

Developexpressions for the mole fractions of reacting species as functions of the reaction coordinate for:
(a) A system initially containing $2 \mathrm{~mol} \mathrm{NH}_3$ and $5 \mathrm{~mol} \mathrm{O}_2$ and undergoing the reaction:
$$
4 \mathrm{NH}_3(\mathrm{~g})+5 \mathrm{O}_2(\mathrm{~g}) \rightarrow 4 \mathrm{NO}(\mathrm{g})+6 \mathrm{H}_2 \mathrm{O}(\mathrm{g})
$$
(b) A system initially containing $3 \mathrm{~mol} \mathrm{H}_2 \mathrm{~S}$ and $5 \mathrm{~mol} \mathrm{O}_2$ and undergoing the reaction:
$$
2 \mathrm{H}_2 \mathrm{~S}(\mathrm{~g})+3 \mathrm{O}_2(\mathrm{~g}) \rightarrow 2 \mathrm{H}_2 \mathrm{O}(\mathrm{g})+2 \mathrm{SO}_2(\mathrm{~g})
$$
(c) A system initially containing $3 \mathrm{~mol} \mathrm{NO}_2, 4 \mathrm{~mol} \mathrm{NH}$, and $1 \mathrm{~mol} \mathrm{~N}_2$ and undergoing the reaction:
$$
6 \mathrm{NO}_2(g)+8 \mathrm{NH}_3(g) \rightarrow 7 \mathrm{~N}_2(g)+12 \mathrm{H}_2 \mathrm{O}(g)
$$

Ronald Prasad
Ronald Prasad
Numerade Educator
02:52

Problem 1

Developexpressions for the mole fractions of reacting species as functions of the reaction coordinate for:
(a) A system initially containing $2 \mathrm{~mol} \mathrm{NH}_3$ and $5 \mathrm{~mol} \mathrm{O}_2$ and undergoing the reaction:
$$
4 \mathrm{NH}_3(\mathrm{~g})+5 \mathrm{O}_2(\mathrm{~g}) \rightarrow 4 \mathrm{NO}(\mathrm{g})+6 \mathrm{H}_2 \mathrm{O}(\mathrm{g})
$$
(b) A system initially containing $3 \mathrm{~mol} \mathrm{H}_2 \mathrm{~S}$ and $5 \mathrm{~mol} \mathrm{O}_2$ and undergoing the reaction:
$$

Angela Caffey
Angela Caffey
Sam Houston State University
02:06

Problem 2

A system initially containing $2 \mathrm{~mol} \mathrm{C}_2 \mathrm{H}_4$ and $3 \mathrm{~mol} \mathrm{O}_2$ undergoes the reactions:
$$
\begin{gathered}
\mathrm{C}_2 \mathrm{H}_4(\mathrm{~g})+\frac{1}{2} \mathrm{O}_2(\mathrm{~g}) \rightarrow\left\langle\left(\mathrm{CH}_2\right)_2\right\rangle \mathrm{O}(\mathrm{g}) \\
\mathrm{C}_2 \mathrm{H}_4(\mathrm{~g})+3 \mathrm{O}_2(\mathrm{~g}) \rightarrow 2 \mathrm{CO}_2(\mathrm{~g})+2 \mathrm{H}_2 \mathrm{O}(\mathrm{g})
\end{gathered}
$$

Develop expressions for the mole fractions of the reacting species as functions of the reaction coordinates for the two reactions.

Lottie Adams
Lottie Adams
Numerade Educator
02:06

Problem 3

A system formed initially of $2 \mathrm{molCO}_2, 5 \mathrm{molH}_2$, and $1 \mathrm{~mol} \mathrm{CO}$ undergoesthe reactions:
$$
\begin{gathered}
\mathrm{CO}_2(\mathrm{~g})+3 \mathrm{H}_2(\mathrm{~g}) \rightarrow \mathrm{CH}_3 \mathrm{OH}(\mathrm{g})+\mathrm{H}_2 \mathrm{O}(\mathrm{g}) \\
\mathrm{CO}_2(\mathrm{~g})+\mathrm{H}_2(\mathrm{~g}) \rightarrow \mathrm{CO}(\mathrm{g})+\mathrm{H}_2 \mathrm{O}(\mathrm{g})
\end{gathered}
$$

Develop expressions for the mole fractions of the reacting species as functions of the reaction coordinates for the two reactions.

Lottie Adams
Lottie Adams
Numerade Educator
05:52

Problem 4

Consider the water-gas-shift reaction:
$$
\mathrm{H}_2(\mathrm{~g})+\mathrm{CO}_2(\mathrm{~g}) \rightarrow \mathrm{H}_2 \mathrm{O}(\mathrm{g})+\mathrm{CO}(g)
$$

At high temperatures and low to moderate pressures the reacting species form an idealgas mixture. Application of the summability equation to Eq. (11.26) yields:
$$
G=\sum_i y_i G_i+R T \sum_i y_i \ln y_i
$$

When the Gibbs energies of the elements in their standard states are set equal to zero, $G_i=\Delta G_{f_i}^{\circ}$ for each species, and then:
$$
G=\sum_i y_i \Delta G_{f_i}^{\circ}+R T \sum_i y_i \ln y_i
$$

At the beginning of Sec. 13.2 we noted that Eq. (14.64) is a criterion of equilibrium. Applied to the water-gas-shiftreaction with the understandingthat $T$ and $P$ are constant, this equation becomes:
$$
d G^t=d(n G)=n d G+G d n=0 \quad n \frac{d G}{d \varepsilon}+G \frac{d n}{d \varepsilon}=0
$$

Here, however, $d n / d \varepsilon=0$. The equilibrium criterion therefore becomes:
$$
\frac{d G}{d \varepsilon}=0
$$

Once the $y_i$ are eliminated in favor of $\varepsilon$, Eq. (A) relates G to $E$. Data for $\Delta G_{f_i}^{\circ}$ for the compounds of interest are given with Ex. 13.13. For a temperature of $1000 \mathrm{~K}$ (the reaction is unaffected by $P$ ) and for a feed of $l \mathrm{~mol} \mathrm{H}_2$ and $l \mathrm{~mol} \mathrm{CO}_2$ :
(a) Determine the equilibrium value of $\varepsilon$ by application of Eq. (B).
(b) Plot G vs. $\varepsilon$, indicating the location of the equilibrium value of $\varepsilon$ determined in (a).

Matthew Hurlock
Matthew Hurlock
Numerade Educator
01:08

Problem 5

Rework $\mathrm{Pb}, 13.4$ for a temperature of:
(a) $1100 \mathrm{~K} ;$ (b) $1200 \mathrm{~K} ;$ (c) $1300 \mathrm{~K}$.

Adriano Chikande
Adriano Chikande
Numerade Educator
01:26

Problem 6

Use the method of equilibrium constants to verify the value of $\varepsilon$ found as an answer in one of the following:
(a) $\mathrm{Pb} .13 .4 ;(b) \mathrm{Pb} .13 .5(a)$; (c) Pb. 13.5(b); (d) $\mathrm{Pb} .13 .5(c)$.

David Collins
David Collins
Numerade Educator
05:04

Problem 7

Develop a general equation for the standard Gibbs-energy change of reaction $\Delta G^{\circ}$ as a function of temperature for one of the reactions given in parts $(a),(f)$, (i), $(n),(r),(t)$, $(u),(x)$, and $(y)$ of $\mathrm{Pb} .4 .21$.

Lucas Pressley
Lucas Pressley
Numerade Educator
03:25

Problem 8

For ideal gases, exact mathematical expressions can be developed for the effect of $T$ and $P$ on $\varepsilon_e$. For conciseness, let $\prod_i\left(y_i\right)^{v_i} \equiv K_y$. Then:
$$
\left(\frac{\partial \varepsilon_e}{\partial T}\right)_P=\left(\frac{\partial K_y}{\partial T}\right)_P \frac{d \varepsilon_e}{d K_y} \quad \text { and } \quad\left(\frac{\partial \varepsilon_e}{\partial P}\right)_T=\left(\frac{\partial K_y}{\partial P}\right)_T \frac{d \varepsilon_e}{d K_y}
$$

Use Eqs. (13.28) and (13.14), to show that:
(a) $\left(\frac{\partial \varepsilon_e}{\partial T}\right)_P=\frac{K_y}{R T^2} \frac{d \varepsilon_e}{d K_y} \Delta H^{\circ}$
(b) $\left(\frac{\partial \varepsilon_e}{\partial P}\right)_T=\frac{K_y}{P} \frac{d \varepsilon_e}{d K_y}(-v)$
(c) $d \varepsilon_e / d K_y$ is always positive. (Note: It is equally valid and perhaps easier to show that the reciprocal is positive.)

Amit Srivastava
Amit Srivastava
Numerade Educator
05:57

Problem 9

For the ammonia synthesis reaction written:
$$
\frac{1}{2} \mathrm{~N}_2(g)+\frac{3}{2} \mathrm{H}_2(g) \rightarrow \mathrm{NH}_3(g)
$$
with $0.5 \mathrm{~mol} \mathrm{~N}_2$ and $1.5 \mathrm{~mol} \mathrm{H}_2$ as the initial amounts of reactants and with the assumption that the equilibrium mixture is an ideal gas, show that:
$$
\varepsilon_e=1-\left(1+1.299 K \frac{P}{P^{\circ}}\right)^{-1 / 2}
$$

James Kiss
James Kiss
Numerade Educator
16:44

Problem 10

Peter, Paul, and Mary, members of a thermodynamicsclass, are asked to find the equilibrium composition at a particular $\mathrm{T}$ and $\mathrm{P}$ and for given initial amounts of reactants for the following gas-phase reaction:
$$
2 \mathrm{NH}_3+3 \mathrm{~N} 0 \rightarrow 3 \mathrm{H}_2 \mathrm{O}+\frac{5}{2} \mathrm{~N}_2
$$

Each solves the problem correctly in a different way. Mary bases her solution on reaction (A) as written. Paul, who prefers whole numbers, multiplies reaction (A) by 2 :
$$
4 \mathrm{NH}_3+6 \mathrm{NO} \rightarrow 6 \mathrm{H}_2 \mathrm{O}+5 \mathrm{~N}_2
$$

Peter, who usually does things backward, deals with the reaction:
$$
3 \mathrm{H}_2 \mathrm{O}+\frac{5}{2} \mathrm{~N}_2 \rightarrow 2 \mathrm{NH}_3+3 \mathrm{~N} 0
$$

Write the chemical-equilibriumequations for the three reactions, indicate how the equilibrium constants are related, and show why Peter, Paul, and Mary all obtain the same result.

Ronald Prasad
Ronald Prasad
Numerade Educator
01:05

Problem 11

The following reaction reaches equilibrium at $773.15 \mathrm{~K}\left(500^{\circ} \mathrm{C}\right)$ and 2 bar;
$$
4 \mathrm{HCl}(\mathrm{g})+\mathrm{O}_2(\mathrm{~g}) \rightarrow 2 \mathrm{H}_2 \mathrm{O}(\mathrm{g})+2 \mathrm{Cl}_2(\mathrm{~g})
$$

If the system initially contains $5 \mathrm{~mol} \mathrm{HCl}$ for each mole of oxygen, what is the composition of the system at equilibrium? Assume ideal gases.

Eileen Sullivan
Eileen Sullivan
Numerade Educator
01:53

Problem 12

The following reaction reaches equilibrium at $923.15 \mathrm{~K}\left(650^{\circ} \mathrm{C}\right)$ and atmospheric pressure:
$$
\mathrm{N}_2(g)+\mathrm{C}_2 \mathrm{H}_2(g)-2 \mathrm{HCN}(g)
$$

If the system initially is an equimolar mixture of nitrogen and acetylene, what is the composition of the system at equilibrium? What would be the effect of doubling the pressure? Assume ideal gases.

Crystal Wang
Crystal Wang
Numerade Educator
03:14

Problem 13

The following reaction reaches equilibrium at $623.15 \mathrm{~K}\left(350^{\circ} \mathrm{C}\right) 3$ bar:
$$
\mathrm{CH}_3 \mathrm{CHO}(\mathrm{g})+\mathrm{H}_2(\mathrm{~g}) \rightarrow \mathrm{C}_2 \mathrm{H}_5 \mathrm{OH}(\mathrm{g})
$$

If the system initially contains $1.5 \mathrm{~mol} \mathrm{H}_2$ for each mole of acetaldehyde, what is the composition of the system at equilibrium? What would be the effect of reducing the pressure to 1 bar? Assume ideal gases.

Adriano Chikande
Adriano Chikande
Numerade Educator
04:28

Problem 14

The following reaction reaches equilibrium at $923.15 \mathrm{~K}\left(650^{\circ} \mathrm{C}\right)$ and atmospheric pressure:
$$
\mathrm{C}_6 \mathrm{H}_5 \mathrm{CH}: \mathrm{CH}_2(\mathrm{~g})+\mathrm{H}_2(\mathrm{~g}) \rightarrow \mathrm{C}_6 \mathrm{H}_5 \cdot \mathrm{C}_2 \mathrm{H}_5(g)
$$

If the system initially contains $1.5 \mathrm{~mol} \mathrm{H}_2$ for each mole of styrene, what is the composition of the system at equilibrium? Assume ideal gases.

Shubham Kumar
Shubham Kumar
Numerade Educator
View

Problem 15

The gas stream from a sulfur burner is composed of $15-\mathrm{mol}-\% \mathrm{SO}_2, 20-\mathrm{mol}-\% \mathrm{O}_2$, and $65-\mathrm{mol}-\% \mathrm{~N}_2$. This gas stream at 1 bar and $753.15 \mathrm{~K}\left(480^{\circ} \mathrm{C}\right)$ enters a catalytic converter, where the $\mathrm{SO}_2$ is further oxidized to $\mathrm{SO}_3$. Assuming that the reaction reaches equilibrium, how much heat must be removed from the converter to maintain isothermal conditions? Base your answer on $1 \mathrm{~mol}$ of entering gas.

Aishwarya Krishnakumar
Aishwarya Krishnakumar
Numerade Educator
01:50

Problem 16

For the cracking reaction,
$$
\mathrm{C}_3 \mathrm{H}_8(\mathrm{~g}) \rightarrow \mathrm{C}_2 \mathrm{H}_4(\mathrm{~g})+\mathrm{CH}_4(\mathrm{~g})
$$
the equilibrium conversion is negligible at $300 \mathrm{~K}$, but becomes appreciable at temperatures above $500 \mathrm{~K}$. For a pressure of 1 bar, determine:
(a) The fractional conversion of propane at $625 \mathrm{~K}$.
(b) The temperature at which the fractional conversion is $85 \%$.

Penny Riley
Penny Riley
Numerade Educator
03:10

Problem 17

Ethylene is produced by the dehydrogenation of ethane. If the feed includes $0.5 \mathrm{~mol}$ of steam (an inert diluent) per mole of ethane and if the reaction reaches equilibrium at $1100 \mathrm{~K}$ and $1 \mathrm{bar}$, what is the composition of the product gas on a water-freebasis?

Shalini Tyagi
Shalini Tyagi
Numerade Educator
08:29

Problem 18

The production of 1,3-butadiene can be carried out by the dehydrogenation of 1-butene:
$$
\mathrm{C}_2 \mathrm{H}_5 \mathrm{CH}: \mathrm{CH}_2(\mathrm{~g}) \rightarrow \mathrm{CH}_2: \mathrm{CHCH}_2 \mathrm{CH}_2(\mathrm{~g})+\mathrm{H}_2(g)
$$

Side reactions are suppressed by the introduction of steam. If equilibrium is attained at $950 \mathrm{~K}$ and 1 bar and if the reactor product contains $10-\mathrm{mol}-\% 1,3$-butadiene, find:
(a) The mole fractions of the other species in the product gas.
(b) The mole fraction of steam required in the feed.

Narayan Hari
Narayan Hari
Numerade Educator
08:29

Problem 19

The production of 1,3-butadiene can be carried out by the dehydrogenation of $n$-butane:
$$
\mathrm{C}_4 \mathrm{H}_{10}(\mathrm{~g}) \rightarrow \mathrm{CH}_2: \mathrm{CHCH}_2 \mathrm{CH}_2(\mathrm{~g})+2 \mathrm{H}_2(\mathrm{~g})
$$

Side reactions are suppressed by the introduction of steam. If equilibrium is attained at $925 \mathrm{~K}$ and 1 bar and if the reactor product contains 12-mol-\%1,3-butadiene, find:
(a) The mole fractions of the other species in the product gas.
(b) The mole fraction of steam required in the feed.

Narayan Hari
Narayan Hari
Numerade Educator
01:18

Problem 20

For the ammonia synthesis reaction,
$$
\frac{1}{2} \mathrm{~N}_2(g)+\frac{3}{2} \mathrm{H}_2(g) \rightarrow \mathrm{NH}_3(g)
$$
the equilibrium conversion to ammonia is large at $300 \mathrm{~K}$, but decreases rapidly with increasing T. However, reaction rates become appreciable only at higher temperatures. For a feed mixture of hydrogen and nitrogen in the stoichiometric proportions,
(a) What is the equilibrium mole fraction of ammonia at 1 bar and $300 \mathrm{~K}$ ?
(h) At what temperature does the equilibrium mole fraction of ammonia equal 0.50 for a pressure of $1 \mathrm{bar}$ ?
(c) At what temperature does the equilibrium mole fraction of ammonia equal 0.50 for a pressure of $100 \mathrm{bar}$, assuming the equilibrium mixture is an ideal gas?
(d) At what temperature does the equilibrium mole fraction of ammonia equal 0.50 for a pressure of 100 bar, assuming the equilibrium mixture is an ideal solution of gases?

Lottie Adams
Lottie Adams
Numerade Educator
05:15

Problem 21

For the methanol synthesis reaction,
$$
\mathrm{CO}(\mathrm{g})+2 \mathrm{H}_2(\mathrm{~g}) \rightarrow \mathrm{CH}_3 \mathrm{OH}(\mathrm{g})
$$
the equilibrium conversion to methanol is large at $300 \mathrm{~K}$, but decreases rapidly with increasing T. However, reaction rates become appreciable only at higher temperatures. For a feed mixture of carbon monoxide and hydrogen in the stoichiometric proportions, (a) What is the equilibrium mole fraction of methanol at 1 bar and $300 \mathrm{~K}$.
(b) At what temperature does the equilibrium mole fraction of methanol equal 0.50 for a pressure of 1 bar?
(c) At what temperature does the equilibrium mole fraction of methanol equal 0.50 for a pressure of 100 bar, assuming the equilibrium mixture is an ideal gas?
(d) At what temperature does the equilibrium mole fraction of methanol equal 0.50 for a pressure of $100 \mathrm{bar}$, assuming the equilibrium mixture is an ideal solution of gases?

Ronald Prasad
Ronald Prasad
Numerade Educator
03:02

Problem 22

Limestone $\left(\mathrm{CaCO}_3\right)$ decomposes upon heating to yield quicklime $(\mathrm{CaO})$ and carbon dioxide. At what temperature is the decomposition pressure of limestone 1(atm)?

Daniel Kim
Daniel Kim
Numerade Educator
01:35

Problem 23

Ammonium chloride $\left[\mathrm{NH}_4 \mathrm{Cl}(s)\right]$ decomposes upon heating to yield a gas mixture of ammonia and hydrochloric acid. At what temperature does ammonium chloride exert a decomposition pressure of 1.5 bar? For $\mathrm{NH}_4 \mathrm{Cl}(s), \Delta H_{f_{298}}^{\circ}=-314430 \mathrm{~J} \mathrm{~mol}^{-1}$ and $\Delta G_{f_{29 \mathrm{~A}}}^{\circ}=-202870 \mathrm{~J} \mathrm{~mol}^{-1}$.

Teesta Dasgupta
Teesta Dasgupta
University of Pittsburgh - Main Campus
01:23

Problem 24

A chemically reactive system contains the following species in the gas phase: $\mathrm{NH}_3, \mathrm{NO}$, $\mathrm{NO}_2, \mathrm{O}_2$, and $\mathrm{H}_2 \mathrm{O}$. Determine a complete set of independent reactions for this system. How many degrees of freedom does the system have?

Stephen Ho
Stephen Ho
Numerade Educator
03:08

Problem 25

The relative compositions of the pollutants $\mathrm{NO}$ and $\mathrm{NO}_2$ in air are governed by the reaction,
$$
\mathrm{NO}+\frac{1}{2} \mathrm{O}_2 \rightarrow \mathrm{NO}_2
$$

For air containing $21-\mathrm{mol}-\% \mathrm{O}_2$ at $298.15 \mathrm{~K}\left(25^{\circ} \mathrm{C}\right)$ and 1.0133 bar, what is the concentration of $\mathrm{NO}$ in parts per million if the total concentration of the two nitrogen oxides is 5 ppm?

Ronald Prasad
Ronald Prasad
Numerade Educator
04:13

Problem 26

Consider the gas-phase oxidation of ethylene to ethylene oxide at a pressure of $l$ bar with $25 \%$ excess air. If the reactantsenter the process at $298.15 \mathrm{~K}\left(25^{\circ} \mathrm{C}\right)$, if the reaction proceeds adiabatically to equilibrium, and if there are no side reactions, determine the composition and temperature of the product stream from the reactor.

Lewis Rose
Lewis Rose
Numerade Educator
11:01

Problem 27

Carbon black is produced by the decomposition of methane:
$$
\mathrm{CH}_4(\mathrm{~g}) \rightarrow \mathrm{C}(s)+2 \mathrm{H}_2(g)
$$

For equilibrium at $923.15 \mathrm{~K}\left(650^{\circ} \mathrm{C}\right)$ and $l$ bar,
(a) What is the gas-phase composition if pure methane enters the reactor, and what fraction of the methane decomposes?
(b) Repeat part $(a)$ if the feed is an equimolar mixture of methane and nitrogen.

Jincy M  Saji
Jincy M Saji
Numerade Educator
01:27

Problem 28

Consider the reactions,
$$
\begin{gathered}
\frac{1}{2} \mathrm{~N}_2(g)+\frac{1}{2} \mathrm{O}_2(g) \rightarrow \mathrm{NO}(g) \\
\frac{1}{2} \mathrm{~N}_2(g)+\mathrm{O}_2(g) \rightarrow \mathrm{NO}_2(g)
\end{gathered}
$$

If these reactionscome to equilibrium after combustion in an internal-combustionengine at $2000 \mathrm{~K}$ and 200 bar, estimate the mole fractions of $\mathrm{NO}$ and $\mathrm{NO}_2$ present for mole fractions of nitrogen and oxygen in the combustion products of 0.70 and 0.05 .

Penny Riley
Penny Riley
Numerade Educator
04:57

Problem 29

Oil refineries frequently have both $\mathrm{H}_2 \mathrm{~S}$ and $\mathrm{SO}_2$ to dispose of. The following reaction suggests a means of getting rid of both at once:
$$
2 \mathrm{H}_2 \mathrm{~S}(g)+\mathrm{SO}_2(g) \rightarrow 3 \mathrm{~S}(s)+2 \mathrm{H}_2 \mathrm{O}(g)
$$

For reactants in the stoichiometric proportion, estimate the percent conversion of each reactant if the reaction comes to equilibrium at $723.15 \mathrm{~K}\left(450^{\circ} \mathrm{C}\right)$ and 8 bar.

James Kiss
James Kiss
Numerade Educator
20:43

Problem 30

The species $\mathrm{N}_2 \mathrm{O}_4$ and $\mathrm{NO}_2$ as gases attain rapid equilibrium by the reaction:
$$
\mathrm{N}_2 \mathrm{O}_4 \rightarrow 2 \mathrm{NO}_2
$$
(a) For $T=350 \mathrm{~K}$ and $P=5$ bar, calculate the mole fractions of these species in the equilibrium mixture. Assume ideal gases.
(b) If an equilibrium mixture of $\mathrm{N}_2 \mathrm{O}_4$ and $\mathrm{NO}_2$ at the conditions of part (a) flows through a throttle valve to a pressure of 1 bar and through a heat exchanger that restores its initial temperature, how much heat must be exchanged, assuming chemical equilibrium is again attained in the final state? Base the answer on an amount of mixture equivalent to $I \mathrm{~mol}$ of $\mathrm{N}_2 \mathrm{O}_4$, i.e., as though all the $\mathrm{NO}_2$ were present as $\mathrm{N}_2 \mathrm{O}_4$.

Susan Hallstrom
Susan Hallstrom
Numerade Educator
03:44

Problem 31

The following isomerization reaction occurs in the liquid phase:
$$
\mathrm{A} \rightarrow \mathrm{B}
$$
where $\mathrm{A}$ and $\mathrm{B}$ are miscible liquids for which:
$$
G^E / R T=0.1 x_{\mathrm{A}} x_{\mathrm{B}}
$$
If $\Delta G_{298}^{\circ}=-1000 \mathrm{~J} \mathrm{~mol}^{-1}$, what is the equilibrium composition of the mixture at $298.15 \mathrm{~K}\left(25^{\circ} \mathrm{C}\right)$ ? How much error is introduced if one assumes that A and B form an ideal solution?

Sanu Kumar
Sanu Kumar
Numerade Educator
05:52

Problem 32

Hydrogen gas is produced by the reaction of steam with "water gas," an equimolar mixture of $\mathrm{H}_2$ and $\mathrm{CO}$ obtained by the reaction of steam with coal. A stream of "water gas" mixed with steam is passed over a catalyst to convert $\mathrm{CO}$ to $\mathrm{CO}_2$ by the reaction:
$$
\mathrm{H}_2 \mathrm{O}(g)+\mathrm{CO}(g) \rightarrow \mathrm{H}_2(g)+\mathrm{CO}_2(g)
$$

Subsequently, unreacted water is condensed and carbon dioxide is absorbed, leaving a product that is mostly hydrogen. The equilibrium conditions are 1 bar and $800 \mathrm{~K}$.
(a) Would there be any advantage to carrying out the reaction at pressures above 1 bar?
(b) Would increasing the equilibrium temperature increase the conversion of $\mathrm{CO}$ ?
(c) For the given equilibrium conditions, determine the molar ratio of steam to "water gas" $\left(\mathrm{H}_2+\mathrm{CO}\right)$ required to produce a product gas containing only $2-\mathrm{mol}-\% \mathrm{CO}$ after cooling to $293.15 \mathrm{~K}\left(20^{\circ} \mathrm{C}\right)$, where the unreacted $\mathrm{H}_2 \mathrm{O}$ has been virtually all condensed.
(d) Is there any danger that solid carbon will form at the equilibrium conditions by the reaction
$$
2 \mathrm{CO}(g) \rightarrow \mathrm{CO}_2(g)+\mathrm{C}(s)
$$

Matthew Hurlock
Matthew Hurlock
Numerade Educator
02:20

Problem 33

The feed gas to a methanol synthesis reactor is composed of $75-\mathrm{mol}-\% \mathrm{H}_2, 15-\mathrm{mol}-\%$ $\mathrm{CO}, 5-\mathrm{mol}-\% \mathrm{CO}_2$, and $5-\mathrm{mol}-\% \mathrm{~N}_2$. The system comes to equilibrium at $550 \mathrm{~K}$ and 100 bar with respect to the following reactions:
$$
\begin{gathered}
2 \mathrm{H}_2(\mathrm{~g})+\mathrm{CO}(\mathrm{g}) \rightarrow \mathrm{CH}_3 \mathrm{OH}(\mathrm{g}) \\
\mathrm{H}_2(\mathrm{~g})+\mathrm{CO}_2(\mathrm{~g}) \rightarrow \mathrm{CO}(\mathrm{g})+\mathrm{H}_2 \mathrm{O}(\mathrm{g})
\end{gathered}
$$

Assuming ideal gases, determine the composition of the equilibrium mixture.

Lottie Adams
Lottie Adams
Numerade Educator
05:27

Problem 34

"Synthesis gas" may be produced by the catalytic reforming of methane with steam:
$$
\mathrm{CH}_4(\mathrm{~g})+\mathrm{H}_2 \mathrm{O}(\mathrm{g}) \rightarrow \mathrm{CO}(\mathrm{g})+3 \mathrm{H}_2(\mathrm{~g})
$$

The only other reaction considered is:
$$
\mathrm{CO}(\mathrm{g})+\mathrm{H}_2 \mathrm{O}(\mathrm{g}) \rightarrow \mathrm{CO}_2(\mathrm{~g})+\mathrm{H}_2(\mathrm{~g})
$$

Assume equilibrium is attained for both reactions at 1 bar and $1300 \mathrm{~K}$.
(a) Would it be better to carry out the reaction at pressures above 1 bar?
(b) Would it be better to carry out the reaction at temperatures below $1300 \mathrm{~K}$ ?
(c) Estimate the molar ratio of hydrogen to carbon monoxide in the synthesis gas if the feed consists of an equimolar mixture of steam and methane.
(d) Repeat part (c) for a steam to methane mole ratio in the feed of 2.
(e) How could the feed composition be altered to yield a lower ratio of hydrogen to carbon monoxide in the synthesis gas than is obtained in part (c)?
(f) Is there any danger that carbon will deposit by the reaction $2 \mathrm{CO} \rightarrow \mathrm{C}+\mathrm{CO}_2$ under conditions of part (c)? Part (d)? If so, how could the feed be altered to prevent carbon deposition?

Albert T.
Albert T.
Numerade Educator
03:51

Problem 35

Consider the gas-phase isomerization reaction: $A \rightarrow B$.
(a) Assuming ideal gases, develop from Eq. (13.28) the chemical-reactionequilibrium equation for the system.
(b) The result of part (a) should suggest that there is one degree of freedom for the equilibrium state. Upon verifying that the phase rule indicates two degrees of freedom, explain the discrepancy.

Ronald Prasad
Ronald Prasad
Numerade Educator
01:45

Problem 36

A low-pressure, gas-phase isomerizationreaction, $\mathrm{A} \rightarrow \mathrm{B}$, occurs at conditions such that vapor and liquid phases are present.
(a) Prove that the equilibrium state is univariant.
(b) Suppose T is specified. Show how to calculate $x_A, y_A$, and P. State carefully, and justify, any assumptions.

Manik Pulyani
Manik Pulyani
Numerade Educator
03:53

Problem 37

Set up the equations required for solution of Ex. 13.14 by the method of equilibrium constants. Verify that your equations yield the same equilibrium compositions as given in the example.

William Mills
William Mills
Numerade Educator
16:44

Problem 38

Reaction-equilibrium calculations may be useful for estimation of the compositions of hydrocarbon feedstocks. A particular feedstock, available as a low-pressure gas at $500 \mathrm{~K}$, is identified as "aromatic C8." It could in principle contain the $\mathrm{C}_8 \mathrm{H}_{10}$ isomers: $\mathrm{o}$-xylene (OX), m-xylene (MX), p-xylene (PX), and ethylbenzene (EB). Estimate how much of each species is present, assuming the gas mixture has come to equilibrium at $500 \mathrm{~K}$ and low pressure. The following is a set of independent reactions (why?):
$$
\begin{aligned}
& \mathrm{OX} \rightarrow \mathrm{MX} \\
& \mathrm{OX} \rightarrow \mathrm{PX} \\
& \mathrm{OX} \rightarrow \mathrm{EB}
\end{aligned}
$$
(a) Write reaction-equilibriumequations for each equation of the set. State clearly any assumptions.
(b) Solve the set of equations to obtain algebraic expressions for the equilibrium vaporphase mole fractions of the four species in relation to the equilibrium constants, $K_{\mathrm{I}}$, $K_{\mathrm{II}}, K_{\text {III }}$.
(c) Use the data below to determine numerical values for the equilibrium constants at $500 \mathrm{~K}$. State clearly any assumptions.
(d) Determine numerical values for the mole fractions of the four species.
$$
\begin{array}{ccc}
\hline \text { Species } & \mathrm{A} H_{f_{298}}^{\circ} / \mathrm{J} \mathrm{mol}^{-1} & A G_{f_{298}}^{\circ} / \mathrm{J} \mathrm{mol}^{-1} \\
\hline \mathrm{OX}(g) & 19000 & 122200 \\
\operatorname{MX}(g) & 17250 & 118900 \\
\operatorname{PX}(g) & 17960 & 121200 \\
\operatorname{EB}(g) & 29920 & 130890 \\
\hline
\end{array}
$$

Ronald Prasad
Ronald Prasad
Numerade Educator