Biochemistry
Biochemistry
6th Edition
ISBN: 9781305577206
Author: Reginald H. Garrett, Charles M. Grisham
Publisher: Cengage Learning
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Textbook Question
Chapter 4, Problem 6P

Answers to all problems are at the end of this book. Detailed solutions are available in the Student Solutions Manual, Study Guide, and Problems Book.

  1. Calculating Concentrations of Species in Amino Acid Solutions

(Integrates with Chapter 2.) Calculate the concentrations of all ionic species in a 0.25 M solution of histidine at pH 2, pH 6.4, and pH 9.3.

Expert Solution & Answer
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Interpretation Introduction

To propose:

The concentrations of all the species in 0.25 M solution of histidine at pH 2, pH 6.4, and pH 9.3.

Introduction:

Amino acids are so named because they all are weak acids. All amino acids have at least two dissociable hydrogens, (diprotic), and some have three dissociable hydrogens and are triprotic.

Explanation of Solution

To find out the concentrations of the all ionic species at various pH values. First write the Henderson-Hasselbalch equation for each dissociation:

pH =pK1+log[His+][His2+]pH =pK2+log[His0][His+]pH =pK3+log[His][His0]

The total concentration of all species in solution will always be 0.25 M.

  [His2+]+[His+]+[His0]+[His]=0.25M

A pH of 2 is closet to pK1and the Henderson-Hasselbalch equation for the first disassociation will be used:

  pHpK1=log[His+][His2+]  10pHpK1=[His+][His2+][His2+]10pHpK1=[His+]

The value of histidine is 1.8

  [His2+]1021.8=[His+][His2+]100.2=[His+]1.58[His2+]=[His+]

At pH 2, [His2+] and [His+] will be the main species in solution:

          [His2+]+[His+]=0.25M[His2+]+1.58[His2+]=0.25M               2.58[His2+]=0.25M               2.58[His2+]=0.25M                      [His2+]=0.097M

The concentration of His2+ can be used to determine the concentration of His+

1.58(0.097M)=[His+]         0.153M=[His+]

The value of [His0] could be determined from [His+] using the Henderson-Hasselbalch equation for second dissociation. The value of pK2for histidine is 6.0.

          pHpK2=log[His0][His+]             1026.0=[His0]0.153M0.153M(104)=[His0]      1.53×105=[His0]

The value of [His-] using the Henderson-Hasselbalch equation for the third dissociation. The value of pK3for histidine is 9.2

                  pHpK3=log[His][His0]                     1029.2=[His-]1.53×105M(1.53×105)(107.2)=[His]              9.6×1013=[His]

These calculations can be repeated to solve for the concentration of all of the histidine species at pH 6.4. A pH of 6.4 is closet to pK2and the Henderson-Hasselbalch equation for the second dissociation will be used.

  pHpK2=log[His0][His+]  10pHpK2=[His0][His+][His+]10pHpK2=[His0]

The value of pK2for histidine is 6.0.

  [His+]106.46.0=[His0]   [His+]100.4=[His0]    2.51[His+]=[His0]

At pH 6.4, [His+] and [His0] will be the main species in solution:

          [His+]+[His0]=0.25M [His+]+2.51[His+]=0.25M                3.51[His+]=0.25M                       [His+]=0.071M

The concentration of His+ can be used to determine the concentration of His02.51(0.071M)=[His0]          0.179M=[His+]

The value of [His2+] could be determined from [His+] using the Henderson-Hasselbalch equation for first dissociation. The value of pK1for histidine is 1.8.

  pHpK1=log[His+][His2+]   106.41.8=0.071M[His2+]  [His2+]=0.071M[104.6]  [His2+]= 1.78×106M  

The value of [His-] could be determined from [His0] using the Henderson-Hasselbalch equation for third dissociation. The value of pK3for histidine is 9.2.

                pHpK3=log[His][His0]                  106.49.2=[His]0.0179M(0.0179M)(102.8)=[His]             2.84×104= [His]

These calculations can be repeated to solve for the concentration of all of the histidine species at pH 9.3. A pH of 9.3 is closet to pK3and the Henderson-Hasselbalch equation for the third dissociation will be used.

           pHpK3=log[His][His0]           10pHpK3=[His][His0][His0]10pHpK3=[His]

The value of pK3for histidine is 9.2.

  [His0]109.39.2=[His]   [His0]100.1=[His]    1.26[His0]=[His]

At pH 9.3, [His0] and [His-] will be the main species in solution:

          [His0]+[His]=0.25M [His0]+1.26[His0]=0.25M                2.26[His0]=0.25M                       [His0]=0.111M

The concentration of His0can be used to determine the concentration of His-

1.26(0.111M)=[His]       0.139M=[His]

The value of [His+] could be determined from [His0] using the Henderson-Hasselbalch equation for second dissociation. The value of pK2for histidine is 6.0.

  pHpK2=log[His0][His+]    109.36.0=0.111[His+]    [His+]=0.111103.3    [His+]= 5.56×105 M

The value of [His2+] could be determined from [His+] using the Henderson-Hasselbalch equation for first dissociation. The value of pK1for histidine is 1.8.

  pHpK1=log[His+][His2+]    109.31.8=5.56×105M[His2+]    [His2+]=5.56×105M107.5    [His2+]= 1.75×1012 M

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