Chemistry
Chemistry
3rd Edition
ISBN: 9780073402734
Author: Julia Burdge
Publisher: MCGRAW-HILL HIGHER EDUCATION
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Chapter 18, Problem 23QP

Using data from Appendix 2, calculate Δ S rxn º  and  Δ S surr for each of the reactions in Problem 18.11 and determine if each reaction is spontaneous at 25ºC .

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Interpretation Introduction

Interpretation:

The standard entropy change of the reaction and the entropy change of surroundings, for the given reaction and the spontaneity of the given reaction are to be determined.

Concept introduction:

The standard enthalpy change of the reaction, ΔHrxno, is calculated using the followingexpression:

ΔHrxno=nΔHfo(product)mΔHfo(reactant)

Here, ΔHrxno is the standard enthalpy change for the reaction, ΔHfo is the standard enthalpy change for the formation of the substance, n is the stoichiometric coefficient of product, and m is the stoichiometric coefficient of reactant.

Answer to Problem 23QP

Solution:

The standard entropy change of the reaction is 75.6J/molK.

The entropy change of the surrounding is 185J/molK.

The reaction isspontaneous.

The standard entropy change of the reaction is 215.8J/molK.

The entropy change of the surrounding is 304J/molK.

The reaction is not spontaneous.

The standard entropy change of the reaction is 98.2J/molK.

The entropy change of the surrounding is 1.46×103J/molK.

The reaction is not spontaneous.

The standard entropy change of the reaction is 282J/molK.

The entropy change of the surrounding is 7.20×103J/molK.

The reaction is spontaneous.

Explanation of Solution

a) PCl3(l)+Cl2(g)PCl5(g)

Calculate entropy change of the universe for the given reaction.

PCl3(l)+Cl2(g)PCl5(g)

The entropy change of the universe for this reaction is calculated using the following expression:

ΔSsurr=ΔHsysT

Here, ΔHsys is the enthalpy changes of the system, T is the temperature.

The enthalpy change of the system ΔHsys is calculated using the following expression:

ΔHsys=ΔHrxno

The standard enthalpy change of the reaction ΔHrxno is calculated using the following expression:

ΔHrxno=nΔHfo(product)mΔHfo(reactant)

Here, ΔHrxno is the standard enthalpy change for the reaction, ΔHfo is the standard enthalpy change for the formation of the substance, n is the stoichiometric coefficient of product, and m is the stoichiometric coefficient of reactant.

ΔHrxno=(ΔHfo[PCl5])(ΔHfo[PCl3]+ΔHfo[Cl2])

From appendix 2, the standard enthalpy change of formation for the substances are as follows:

ΔHfo[PCl5(s)]=374.9kJ/mol

ΔHfo[PCl3(l)]=319.7kJ/mol

ΔHfo[Cl2(g)]=0kJ/mol

Substitute the standard enthalpy change of the formation value of the substance in the above expression,

ΔHrxno=[(374.9kJ/mol)][(319.7kJ/mol)+(0)]=55.2kJ/molΔHsys=55.2kJ/mol

The standard entropy change for this reaction is calculated using the following expression:

ΔSsurr=ΔHsysT

Substitute the value of T and ΔHsys in the above expression,

ΔSsurr=(55.2kJ/mol)298K=0.185kJ/molK               =185J/molK

Therefore, the entropy change of the surrounding is 185J/molK.

Calculate the standard entropy change of the given reaction.

PCl3(l)+Cl2(g)PCl5(g)

The standard entropy change for this reaction is calculated using the following expression:

ΔSrxno=nSo(product)mSo(reactant)

Here, ΔSrxno is the standard entropy change for the reaction, ΔSo is the standard entropy change of the substance, n is the stoichiometric coefficient of product,

and m is the stoichiometric coefficient of reactant.

ΔSrxno=(S0[PCl5])(So[PCl3]+So[Cl2])

From appendix 2, the standard entropy values for the substances are as follows:

So[PCl5(g)]=364.5J/molK

So[Cl2(g)]=223.0J/molK

So[PCl3(l)]=217.1J/molK

Substitute the standard entropy value of the substance in the above expression,

ΔSrxno=[(364.5J/molK)][(223.0J/molK)+(217.1J/molK)]=75.6J/molK

Therefore, the standard entropy change for this reaction is 75.6J/molK.

Calculate the entropy change of the universe.

The entropy change of the universe is calculate using the following expression:

ΔSuniv=ΔSsys+ΔSsurr

Substitute the value of ΔSsys and ΔSsurr in the above expression,

ΔSuniv=185J/molK+(75.6J/mol.K)             =109J/molK

Therefore, entropy change of the universe for this reaction is 109J/molK .

For the spontaneity of reaction, the value of ΔSuniv should be positive.

The entropy change of the universe for this reaction is positive.

ΔSunivispositive

Therefore, the reaction isspontaneous.

b) 2HgO(s)2Hg(l)+O2(g)

Calculate entropy change of the universe for the given reaction.

2HgO(s)2Hg(l)+O2(g)

The entropy change of the universe for this reaction is calculated using the following expression:

ΔSsurr=ΔHsysT

Here, ΔHsys is the enthalpy changes of the system, T is the temperature.

The enthalpy change of the system ΔHsys is calculated using the expression as follows:

ΔHsys=ΔHrxno

The standard enthalpy change of the reaction ΔHrxno is calculated using the following expression:

ΔHrxno=nΔHfo(product)mΔHfo(reactant)

Here, ΔHrxno is the standard enthalpy change for the reaction, ΔHfo is the standard enthalpy change for the formation of the substance, n is the stoichiometric coefficient of product, and m is the stoichiometric coefficient of reactant.

ΔHrxno=(2×ΔHfo[Hg]+ΔHfo[O2])(2×ΔHfo[HgO])

From appendix 2, the standard enthalpy change of the formation for the substances are as follows:

ΔHfo[HgO(s)]=90.7kJ/mol

ΔHfo[Hg(l)]=0kJ/mol

ΔHfo[O2(g)]=0kJ/mol

Substitute the standard enthalpy change of the formation value of the substances in the above expression.

ΔHrxno=[(0)+[(0)]][(90.7kJ/mol)]=90.7kJ/molΔHsys=90.7kJ/mol

The standard entropy change for this reaction is calculated using the following expression:

ΔSsurr=ΔHsysT

Substitute the value of T and ΔHsys in the above expression.

ΔSsurr=(90.7kJ/mol)298K=0.304kJ/molK               =304J/molK

Therefore, the entropy change of the surrounding is 304J/molK.

Calculate the standard entropy change of the given reaction.

2HgO(s)2Hg(l)+O2(g)

The standard entropy change for this reaction is calculated using the following expression:

ΔSrxno=nSo(product)mSo(reactant)

Here, ΔSrxno is the standard entropy change for the reaction, ΔSo is the standard entropy change of the substance, n is the stoichiometric coefficient of product,

and m is the stoichiometric coefficient of reactant.

ΔSrxno=(2×So[Hg(l)]+So[O2(g)])(2×So[HgO(s)])

From appendix 2, the standard entropy value of the substances are as follows:

So[Hg(l)]=77.4J/molK

So[HgO(g)]=72.0J/molK

So[O2(g)]=205.0J/molK

Substitute the standard entropy value of the substance in the above expression,

ΔSrxno=[2×(77.4J/molK)+(205.0J/molK)][2×(72.0J/molK)]=215.8J/molK

Therefore, the standard entropy change for this reaction is 215.8J/molK.

Calculate the entropy change of the universe.

The entropy change of the universe is calculate using the following expression:

ΔSuniv=ΔSsys+ΔSsurr

Substitute the value of ΔSsys and ΔSsurr in the above expression,

ΔSuniv=215.8J/molK+(304J/mol.K)             =88J/molK

Therefore, entropy change of the universe for this reaction is 88J/molK .

For the spontaneity of reaction, the value of ΔSuniv should be positive.

The entropy change of the universe for this reaction is negative.

ΔSunivisnegative

Therefore, the reaction is not spontaneous.

c) H2(g)2H(g)

Calculate entropy change of the universe for the given reaction.

H2(g)2H(g)

The entropy change of the universe for this reaction is calculated using the following expression:

ΔSsurr=ΔHsysT

Here, ΔHsys is the enthalpy changes of the system, T is the temperature.

The enthalpy change of the system ΔHsys is calculated using the following expression:

ΔHsys=ΔHrxno

The standard enthalpy change of the reaction ΔHrxno iscalculated by using bond enthalpy of the element expression as follows:

ΔHrxno=nΔHfo(reactant)mΔHfo(product)

Here, ΔHrxno is the standard enthalpy change for the reaction, ΔHfo is the standard enthalpy change for the formation of the substance, n is the stoichiometric coefficient of product, and m is the stoichiometric coefficient of reactant.

ΔHrxno=(ΔHfo[H2(g)])(ΔHfo[H])

From table 8.6, bond enthalpy of the elements are as follows:

ΔHfo[H(g)]=0kJ/mol

ΔHfo[H2(g)]=436.4kJ/mol

Substitute the standard enthalpy change of the formation value of the substance in the above expression,

ΔHrxno=[(436.4kJ/mol)][(0)]ΔHsystem=436.4kJ/mol

The standard entropy change for this reaction is calculated using the following expression:

ΔSsurr=ΔHsysT

Substitute the value of T and ΔHsys in the above expression,

ΔSsurr=(436.4kJ/mol)298K=1.46kJ/molK               =1.46×103J/molK

Therefore, the entropy change of the surrounding is 1.36×103J/molK.

Calculate the standard entropy change of the given reaction.

H2(g)2H(g)

The standard entropy change for this reaction is calculated using the following expression:

ΔSrxno=nSo(product)mSo(reactant)

Here, ΔSrxno is the standard entropy change for the reaction, ΔSo is the standard entropy change of the substance, n is the stoichiometric coefficient of product,

and m is the stoichiometric coefficient of reactant.

ΔSrxno=(2×So[H(g)])(So[H2(g)])

From the appendix 2 the standard entropy value of the substances are as follows:

So[H2(g)]=131.0J/molK

So[H(g)]=114.6J/molK

Substitute the standard entropy value of the substance in the above expression,

ΔSrxno=[(2)×(114.6J/molK)][(131.0J/molK)]=98.2J/molK

Therefore, the standard entropy change for this reaction is 98.2J/molK.

Calculate the entropy change of the universe.

The entropy change of the universe is calculate using the following expression:

ΔSuniv=ΔSsys+ΔSsurr

Substitute the value of ΔSsys and ΔSsurr in the above expression.

ΔSuniv=98.2J/molK+(1.46×103J/mol.K)             =1.36×103J/molK

Therefore, entropy change of the universe for this reaction is 1.36×103J/molK .

For the spontaneity of reaction, the value of ΔSuniv should be positive.

The entropy change of the universe for this reaction is negative.

ΔSunivisnegative

Therefore, the reaction is not spontaneous.

d) U(s)+3F2(g)UF6(s)

Calculate entropy change of the universe for the given reaction.

U(s)+3F2(g)UF6(s)

The entropy change of the universe for this reaction is calculated using the following expression:

ΔSsurr=ΔHsysT

Here, ΔHsys is the enthalpy changes of the system and T is the temperature.

The enthalpy change of the system ΔHsys is calculated using the following expression:

ΔHsys=ΔHrxno

The standard enthalpy changes of the reaction ΔHrxno is calculated by using bond enthalpy of the element expression as follows:

ΔHrxno=mΔHfo(reactant)nΔHfo(product)

Here, ΔHrxno is the standard enthalpy change for the reaction, ΔHfo is the standard enthalpy change for the formation of the substance, n is the stoichiometric coefficient of product, and m is the stoichiometric coefficient of reactant.

ΔHrxno=(ΔHfo[UF6])(ΔHfo[U]+3×ΔHfo[F2])

From appendix 2, the standard enthalpy change of the formation for the substances are as follows:

ΔHfo[UF6(s)]=2147kJ/mol

ΔHfo[U(s)]=0kJ/mol

ΔHfo[F2(g)]=0kJ/mol

Substitute the standard enthalpy change of the formation value of the substances in the above expression,

ΔHrxno=[(1)×2147kJ/mol][3×(0)+(0)]=2147kJ/molΔHsys=2147kJ/mol

The standard entropy change for this reaction is calculated using the following expression:

ΔSsurr=ΔHsysT

Substitute the value of T and ΔHsys in the above expression,

ΔSsurr=(2147kJ/mol)298K=7.20kJ/molK               =7.20×103J/molK

Therefore, the entropy change of the surrounding is 7.20kJ/molK.

Calculate the standard entropy change of the given reaction.

U(s)+3F2(g)UF6(s)

The standard entropy change for this reaction is calculated using the following expression:

ΔSrxno=nSo(product)mSo(reactant)

Here, ΔSrxno is the standard entropy change for the reaction, ΔSo is the standard entropy change of the substance, n is the stoichiometric coefficient of product,

and m is the stoichiometric coefficient of reactant.

ΔSrxno=(S0[UF6])(So[U]+3×So[F2])

From appendix 2, the standard entropy value of the substances are as follows:

So[UF6(s)]=378J/molK

So[U(s)]=50.21J/molK

So[F2(g)]=0J/molK

Substitute the standard entropy value of the substance in the above expression,

ΔSrxno=[(378J/molK)][(1)×(50.21J/molK)+[(3)×(203.34J/molK)]]=282J/molK

Therefore, the standard entropy change for this reaction is 282J/molK.

Calculate the entropy change of the universe.

The entropy change of the universe is calculate using the following expression:

ΔSuniv=ΔSsys+ΔSsurr

Substitute the value of ΔSsys and ΔSsurr in the above expression,

ΔSuniv=7.20×103J/molK+(282J/mol.K)             =6.92×103J/molK

Therefore, entropy change of the universe for this reaction is 6.92×103J/molK .

For the spontaneity of reaction, the value of ΔSuniv should be positive.

The entropy change of the universe for this reaction is positive.

ΔSunivispositive

Therefore, the reaction is spontaneous.

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Chapter 18 Solutions

Chemistry

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