Quantitative Chemical Analysis
Quantitative Chemical Analysis
9th Edition
ISBN: 9781464135385
Author: Daniel C. Harris
Publisher: W. H. Freeman
Question
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Chapter 19, Problem 19.10P

a)

Interpretation Introduction

Interpretation:

The equations have to be written for [HIn-] and [In2-] in terms of absorbance at given wavelength and also [In2-][HIn-]=RAε434HIn620HInε620In2--RAε434In2-=RIn has to be proved.

Concept Introduction:

Beer law:

A=-logPPo=εcb

where,A-absorbancePo-incidentirradianceandP-transmittedirradianceε-molarabsorptivityc-concentrationandb-pathlength.

To write the equations for [HIn-] and [In2-] in terms of absorbance at given wavelength

To prove [In2-][HIn-]=RAε434HIn620In2-ε620In2--RAε434HIn=RIn

a)

Expert Solution
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Explanation of Solution

A620HIn-620b[HIn-]In2-620b[In2-]A434HIn-434b[HIn-]In2-434b[In2-]

The solution obtained by solving the two above equations are,

[HIn-]=1D(A620εIn2-434b-A434εIn2-620b)[In2-]=1D(A434εHIn-620b-A620εHIn-434b)D=b2(εHIn-620εIn2-434 - εIn2-620εHIn-434)

Divide the expression for [In2-] by expression for [HIn-] . The resultant equation is,

[In2-][HIn-]=A434εHIn-620-A620εHIn-434A620εIn2-434-A434εIn2-620

Divide the numerator and denominator on right side by A434 . The solution is

[In2-][HIn-]=εHIn-620-RaεHIn-434RaεIn2-434In2-620[In2-][HIn-]=RaεHIn-434HIn-620εIn2-620-RaεIn2-434

b)

Interpretation Introduction

Interpretation:

The equations

[HIn-]=FInRIn+1[In2-]=KInFIn[H+](RIn+1) Have to be proved for acid dissociation constant KIn .

To prove KIn = [HIn-]=FInRIn+1[In2-]=KInFIn[H+](RIn+1)

b)

Expert Solution
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Explanation of Solution

For indicator, the mass balance can be given as ,

[HIn-]+[In2-]=FIn

Divide by [HIn-] on both sides ,

[HIn-][HIn-]+[In2-][HIn-]=FIn[HIn-]1+RIn=FIn[HIn-][HIn-]=FInRIn+1

The acid dissociation constant of the indicator is,

KIn=[In2-][H+][HIn-]

Substitute FIn/(RIn+1) for [HIn-] gives,

KIn=[In2-][H+](RIn+1)FIn[In2-]=KInFIn[H+](RIn+)

c)

Interpretation Introduction

Interpretation:

[H+]=KIn/RIn has to be proved.

To prove [H+]=KIn/RIn

c)

Expert Solution
Check Mark

Explanation of Solution

RIn=[In2-][HIn-]

Hence,

KIn=[In2-][H+][HIn-]RIn[H+]

Therefore,

[H+]=KIn/RIn

d)

Interpretation Introduction

Interpretation:

With the help of Carbonic acid dissociation equilibria [HCO3-]=K1[CO2(aq)][H+] and [CO32-]=K1K2[CO2(aq)][H+]2 have to be proved.

To prove [HCO3-]=K1[CO2(aq)][H+] and [CO32-]=K1K2[CO2(aq)][H+]2

d)

Expert Solution
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Explanation of Solution

From the acid dissociation reaction of Carbonic acid, it can be written as,

K1=[HCO3-][H+][CO2(aq)][HCO3]=K1[CO2(aq)][H+]

From the acid dissociation reaction of Bicarbonate, it can be written as,

K2=[CO32-][H+][HCO3-][CO32-]=K2[HCO3-][H+]

Substitute in [HCO3] gives,

[CO32-]=K1K2[CO2(aq)][H+]2

e)

Interpretation Introduction

Interpretation:

The charge balance for the solution has to be determined and substituted in expressions for [HIn-],[In2-],[HCO3-]and[CO32-] .

To determine the charge balance for the solution and substitute the expressions for [HIn-],[In2-],[HCO3-]and[CO32-]

e)

Expert Solution
Check Mark

Explanation of Solution

The charge balance is given as,

[Na+]+[H+]=[OH-]+[HIn-]+2[In2-]+[HCO3-]+2[CO32-]

FNa+[H+]=Kw[H+]+FInRIn+1+2KInFIn[H+]+(RIn+1)+K1[CO2(aq)][H+]+2K1K2[CO2(aq)][H+]2

f)

Interpretation Introduction

Interpretation:

The amount of [CO2(aq)] in sea water has to be found

To find the amount [CO2(aq)] in sea water

f)

Expert Solution
Check Mark

Explanation of Solution

[H+]=KIn/RIn

RIn can be calculated from,

RIn=RAε434HIn620HInε620In2--RAε434In2-=(2.84)(8.00×103)-(0)(1.70×104)-(2.84)(1.90×103)=1.958[H+]=KIn/RIn[H+]=(2.0×10-7)/1.958[H+]=1.02×10-7M

The value of [H+] is substituted into mass balance and an unknown equation of [CO2(aq)] is produced,

FNa+[H+]=Kw[H+]+FInRIn+2KInFIn[H+](RIn+1)+K1[CO2(aq)][H+]+2K1K2[CO2(aq)][H+]292.0×10-6+1.02×10-7=(6.7×10-15)(1.02×10-7)+(50.0×10-6)1.958+1+2(2.0×10-7)(50.0×10-6)(1.02×10-7)(1.958+1)+(3.0×10-7)[CO2(aq)](1.02×10-7)+2(3.0×10-7)(3.3×10-11)[CO2(aq)](1.02×10-7)19.21×10-5=6.56×10-8+1.69×10-5+6.62×10-5+2.94[CO2(aq)]+0.0019[CO2(aq)][CO2(aq)]=3.04×10-6M

g)

Interpretation Introduction

Interpretation:

The ionic strength inside the sensor compartment has to be determined.

To determine the ionic strength inside the sensor compartment

g)

Expert Solution
Check Mark

Explanation of Solution

Na+,HIn-,In2-,HCO3-,CO32-andOH- are present in the solution. If the net cation charge is 92.1μM , the net charge on anion should be 92.1μM and the ionic strength must approximately 92μm10-4M . The activity coefficients are close to 1.00 and hence an ionic strength of 10-4M is low.

The exact ionic strength can be calculated as,

[OH-]=Kw[H+]=0.07μM

[HIn-]=FInRIn+1=16.9μm[In2-]=KInFIn[H+](RIn+1)=33.1μm[HCO3-]=K1[CO2(aq)][H+]=2.94[CO2(aq)]=8.9μM[CO32-]=K1K2[CO2(aq)][H+]2=0.0019[CO2(aq)]=0.003μM

Ionic strength =

12cizi2={[Na+].12+[H+].12+[OH-].12+[In2-].22+[HCO3-].12+[CO32-].22+[CO32-].22}=125μM

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