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SECTION 8
ELECTROLYTES,ELECTROMOTIVE FORCE,ANDCHEMICAL EQUILIBRIUM
8.1 ACTIVITY COEFFICIENTS8.2Table 8.1 Individual Activity Coefficientsof Ions in Water at 25
C8.3Table 8.2 Approximate Effective Ionic Radii in AqueousSolutionsat 25
C8.4Table 8.3 Constantsof the Debye-Hu¨ckel Equation from 0 to 100
C8.5Table 8.4 Individual Ionic Activity Coefficientsat Higher Ionic Strengthsat25
C8.58.2 EQUILIBRIUM CONSTANTS8.6Table 8.5 IonicProduct Constant of Water8.6Table 8.6 Solubility Product Constants8.68.2.1 Proton-Transfer Reactions8.17Table 8.7 Proton Transfer Reactionsof InorganicMaterialsin Water at 25
C8.18Table 8.8 Valuesof Organic Materialsin Water at 25
Cp
8.24Table 8.9 Selected Equilibrium Constantsin AqueousSolution at VariousTemperatures8.73Table 8.10 Propertiesof Common Acid-Base Solvents8.80Table 8.11 Values for Proton-Transfer Reactionsin NonaqueousSolventsp
8.818.2.2 Formation Constantsof Metal Complexes8.82Table 8.12 Cumulative Formation Constantsfor Metal ComplexeswithInorganicLigands8.83Table 8.13 Cumulative Formation Constantsfor Metal Complexeswith OrganicLigands8.888.3 BUFFER SOLUTIONS8.1048.3.1 Standard Reference pH Buffer Solutions8.104Table 8.14 National Bureau of Standards(U.S.) Reference pH Buffer Solutions8.105Table 8.15 Compositionsof Standard pH Buffer Solutions[National Bureau ofStandards(U.S.)]8.1068.3.2 Standardsfor pH Measurement of Blood and Biological Media8.106Table 8.16 Composition and pH Valuesof Buffer Solutions8.107Table 8.17 Standard Reference Values for the Measurement of Acidity inpH*
50 Weight Percent Methanol-Water8.109Table 8.18 pH* Valuesfor Buffer Solutionsin Alcohol-Water Solventsat 25
C8.1098.3.3 Buffer SolutionsOther Than Standards8.110Table 8.19 pH Valuesof Biological and Other Buffers for Control Purposes8.1108.4 REFERENCE ELECTRODES8.113Table 8.20 Potentialsof Reference Electrodesin Volts as a Function ofTemperature8.113Table 8.21 Potentialsof Reference Electrodes(in Volts) at 25
C for Water–Organic Solvent Mixtures8.1148.4.1 ElectrometricMeasurement of pH8.115Table 8.22 Valuesof 2.3026
RT 
/
at Several Temperatures8.1158.5 INDICATORS8.116Table 8.23 Indicatorsfor AqueousAcid-Base Titrations8.116Table 8.24 Mixed Indicators8.1188.1
 
8.2
SECTION 8
Table 8.25 Fluorescent Indicators8.120Table 8.26 Selected List of Oxidation-Reduction Indicators8.1228.6 ELECTRODE POTENTIALS8.124Table 8.27 Potentialsof the Elementsand Their Compoundsat 25
C8.124Table 8.28 Potentialsof Selected Half-Reactionsat 25
C8.137Table 8.29 Overpotentialsfor Common Electrode Reactionsat 25
C8.140Table 8.30 Half-Wave Potentialsof InorganicMaterials8.141Table 8.31 Half-Wave Potentials(vs. Saturated Calomel Electrode) of OrganicCompoundsat 25
C8.1468.7 CONDUCTANCE8.157Table 8.32 Limiting Equivalent Ionic Conductancesin AqueousSolutions8.157Table 8.33 Standard Solutionsfor Calibrating Conductivity Vessels8.160Table 8.34 Electrical Conductivity of Various Pure Liquids8.161Table 8.35 Equivalent Conductivitiesof Electrolytesin AqueousSolutionsat18
C8.163Table 8.36 Conductivity of Very Pure Water at VariousTemperaturesand theEquivalent Conductancesof Hydrogen and Hydroxyl Ions8.1688.7.1 Common Conductance Relations8.168
8.1 ACTIVITY COEFFICIENT
Although it is not possible to measure an individual ionic activity coefficient,
i
, it may be estimatedfrom the following equation of the Debye-Hu¨ckel theory:
2
 Az
i
p
log
i
1
 Ba˚
p
where
is the ionic strength of the medium, and
a˚ 
is the ion-size parameter—the effective ionicradius (Table 8.2). The values of 
A
and
B
vary with the temperature and dielectric constant of thesolvent; values from 0 to 100
C for aqueous medium (
a˚ 
in angstrom units) are listed in Table 8.3.Corresponding values of 
A
and
B
for unit weight of solvent (when employing molality) can beobtained by multiplying the corresponding values for unit volume (molarity units) by the squareroot of the density of water at the appropriate temperature.The ionic strength can be estimated from the summation of the product molarity timesionic charge squared for all the ionic species present in the solution, i.e.,
2
 I 
0.5(
c z
1 12 2
c z
···
c z
).
2 2
i i
Values for the activity coefficients of ions in water at 25
C are given in Table 8.1 in terms of their effective ionic radii.At moderate ionic strengths a considerable improvement is effected by subtracting a term
bI 
fromthe Debye-Hu¨ckel expression;
b
is an adjustable parameter which is 0.2 for water at 25
C. Table 8.4gives the values of the ionic activity coefficients (for
z
i
from 1 to 6) with
a˚ 
taken to be 4.6A˚.In general, the mean ionic activity coefficient is given by
(
 x
 y
)
x y
 f 
f
p
 
ELECTROLYTES, EMF, AND CHEMICAL EQUILIBRIUM
8.3TABLE 8.1
Individual Activity Coefficients of Ions in Water at 25
CEffective Ionic Radii
a˚ 
(in A˚)ƒ
i
at Ionic Strength of 0.001 0.005 0.01 0.05 0.1Univalent Ions9 0.967 0.933 0.914 0.86 0.838 0.966 0.931 0.912 0.85 0.827 0.965 0.930 0.909 0.845 0.816 0.965 0.929 0.907 0.835 0.805 0.964 0.928 0.904 0.83 0.794 0.964 0.928 0.902 0.82 0.7753.5 0.964 0.926 0.900 0.81 0.763 0.964 0.925 0.899 0.805 0.7552.5 0.964 0.924 0.898 0.80 0.75Divalent Ions8 0.872 0.755 0.69 0.52 0.457 0.872 0.755 0.685 0.50 0.4256 0.870 0.749 0.675 0.485 0.4055 0.868 0.744 0.67 0.465 0.384.5 0.868 0.741 0.663 0.45 0.364 0.867 0.740 0.660 0.445 0.355Trivalent Ions6 0.731 0.52 0.415 0.195 0.135 0.728 0.51 0.405 0.18 0.1154 0.725 0.505 0.395 0.16 0.095Tetravalent Ions11 0.588 0.35 0.255 0.10 0.0655 0.57 0.31 0.20 0.048 0.021Pentavalent Ions9 0.43 0.18 0.105 0.020 0.009
where are the individual ionic activity coefficients, and
x
,
 y
are the charge numbers o
 f 
,
(
 z
,
z
)
the respective ions. In binary electrolyte solution.
 f 
f
p
In ternary electrolytes, e.g., BaCl
2
or K
2
SO
4
,
3 3
2 2
 f 
f
or
f
p
p
In quaternary electrolytes, e.g., LaCl
3
or K
3
[Fe(CN)
6
],
4 4
3 3
 f 
f
or
f
p
p

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