Let the Titrations Begin
Chapter 7
Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 1
Chapter Outline
• Section 7-1 Titrations
• Section 7-2 Titration Calculations
• Section 7-3 Precipitation Titration Curves
• Section 7-4 Titration of a Mixture
• Section 7-5 Calculating Titration Curves with a Spreadsheet
• Section 7-6 End-Point Detection
Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 2
Video: The Phoenix Mars Lander
Titration on Mars (Phoenix Mars Lander)
How can wet chemistry be used to quantify ions in Martian soil?
• ~1 gram of soil was added to “beaker” by a
robotic arm.
• Sulfate was measured by a precipitation
titration with Ba2+.
()
BaCl2 s → Ba2+ + 2Cl−
()
S O 24− + Ba2+ → BaSO 4 s
• The end point of titration is marked by a
sudden increase in Ba2+.
• Titration of two soil samples found ~1.3
(±0.5) wt% sulfate in the soil.
• Other evidence suggests the sulfate is
mostly MgSO4.
Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 3
Section 7-1
Titrations
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Volumetric Analysis
Volumetric analysis: procedures that measure volume of reagents needed to
react with analyte
Titration: increments of reagent solution added until the reaction between
analyte and titrant is complete
• Titrant: reagent solution; usually delivered from a buret
• Analyte: quantity calculated from amount of titrant
consumed in reaction
Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 5
Titrations
Principle Requirements
• The reaction must have a large equilibrium constant.
• The reaction must proceed rapidly.
• Each increment of titrant should be completely and quickly consumed.
• Analyte should be completely used up.
Common titrations rely on:
• Acid-base reactions
• Oxidation-reduction reactions
• Complex formation reactions
• Precipitation reactions
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Figure 7-1 Typical Setup for a Titration
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Equivalence Point
Equivalence point: quantity of added titrant is exact amount necessary for
stoichiometric reaction with the analyte
If unknown contains 5.000 mmol of oxalic acid, the equivalence point is
reached when 2.000 mmol of MnO4− have been added.
Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 8
Equivalence Point vs End Point
Equivalence point: the ideal (theoretical) result based on stoichiometry
End point: actual measurement, marked by a sudden change in physical property
of the solution
For Reaction 7-1, convenient end point = abrupt appearance of purple permanganate in flask
• Prior to equivalence point, all MnO4− accumulates, so solution is purple.
• First trace of purple is the end point. MnO4− is consumed by C2O4H2, so solution is
colorless.
• After equivalence point, purple
End point does not equal equivalence point because extra MnO4− , beyond what
is needed to react with oxalate, is required to exhibit purple color.
Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 9
Titrations: End Point
Methods for Determining End Point
• Detection of a sudden change in voltage (or current) between a
pair of electrodes
• Observation of an indicator color change
• Monitor the absorption of light
Indicator: compound with a physical property (usually color) that
changes abruptly near the equivalence point
• Change caused by disappearance of analyte or appearance of
excess titrant
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Titration Error
Titration error: difference between the end point and the
equivalence point
Blank titration: carry out same titration procedure on similar solution
without the analyte
• Provides an estimate of the titration error
• Subtract blank titration volume from volume observed in the
analytical titration
Video: Dealing with Vague Titration
Endpoints
Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 11
Primary Standards
Validity of analytical result depends on knowing the amount of one of
the reactants.
Primary Standard
• Pure enough and stable enough to be used directly after weighing
(entire mass is considered to be pure reagent)
• 99.9% pure
• Should not decompose during storage
• Stable when dried by heat or vacuum (drying required to remove
traces of water absorbed from atmosphere)
• Stoichiometry of reaction with titrant must be known
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Box 7-1 Reagent Chemicals and Primary Standards
Chemicals are sold under many grades of purity.
• Few chemicals are sold in high enough purity to be
primary standard grade.
• Reagent grade chemicals meet purity requirements
set by the American Chemical Society (ACS)
Committee on Analytical Reagents.
• Trace metal grade reagents have extremely low
impurities, important for trace analysis of ppm.
The highest quality, commercially available primary standard pure materials
have purities certified to be 100 ± 0.05%.
Appendix K lists primary standards for many elements.
Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 13
Standardization
Many reagents used as titrants are not available as primary standards (e.g., HCl).
Standardization
• Prepare a titrant with approximately the desired concentration and use it to
titrate a primary standard
• Method can be used to determine the concentration of the titrant
• Validity of analytical result ultimately depends on knowing the concentration
of the primary standard
Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 14
Article: Gravimetric titration
Types of Titrations
Direct titration: add titrant to analyte until reaction complete
Back titration: (1) add known excess of one standard reagent to the analyte;
(2) titrate excess with second standard reagent
• Useful when end point of back titration is clearer than direct titration
• Useful when an excess of the first reagent is required for complete reaction
with analyte
Gravimetric titration: measure the mass of titrant solution delivered in
each increment
• Titrant can be delivered from a pipet (units = moles reagent per kg of solution)
• Precision improved from 0.3% with buret to 0.1% with balance
Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 15
Section 7-2
Titration Calculations
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Titration Calculations
Figure 7-1
The key step in any titration calculation is to relate
moles of titrant to moles of analyte.
Keep in mind:
• Units: mmol/mL is the same as mol/L
• Stoichiometry of reaction
Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 17
Example: Standardization of Titrant Followed by
Analysis of Unknown (1 of 7)
The calcium content of urine can be determined by the following procedure:
Step 1 Precipitate Ca2+ with oxalate in basic solution:
Ca2 + C2O24− → Ca(C2O4 ) H2O(s)
Oxalate Calcium oxalate
Step 2 Filter and wash the precipitate with ice-cold water to remove free oxalate,
and dissolve the solid in acid to obtain Ca2+ and H2C2O4 in solution.
Step 3 Heat the solution to 60°C and titrate the oxalic acid with standardized
potassium permanganate until the purple end point of Reaction 7-1 is
observed.
Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 18
Example: Standardization of Titrant Followed by
Analysis of Unknown (2 of 7)
Standardization Suppose that 0.356 2 g of Na2C2O4 is dissolved in a 250.0-mL
volumetric flask. If 10.00 mL of this solution require 48.36 mL of KMnO4 solution
for titration, what is the molarity of the permanganate solution?
Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 19
Example: Standardization of Titrant Followed by
Analysis of Unknown (3 of 7)
Solution: The concentration of the oxalate solution is
0.356 2 g Na2C2O4 /(134.00 g Na2C2O4 /mol)
= 0.010 633 M
0.250 0 L
The moles of C2O24− in 10.00 mL are (0.010 633 mol/L)(0.010 00 L) = 1.0633 × 10−4 mol
= 0.106 33 mmol. Reaction 7-1 requires 2 mol of permanganate for 5 mol of oxalate, so
the MnO4− delivered must have been
2 mol MnO4−
Moles of MnO4− = (1.0633 10 −4 mol C2O24− ) = 0.042 531 mmol
5 mol C2O24−
Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 20
Example: Standardization of Titrant Followed by
Analysis of Unknown (4 of 7)
Solution: The concentration of MnO4− in the titrant is therefore
0.042 531 mmol
Molarity of MnO4− = = 8.794 7 10 −4 M
48.36 mL
Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 21
Example: Standardization of Titrant Followed by
Analysis of Unknown (5 of 7)
Analysis of Unknown Calcium in a 5.00-mL urine sample was precipitated with C2O24− ,
isolated, and redissolved in acid. The sample then required 16.17 mL of standard MnO4−
solution. Find the concentration of Ca2+ in the urine.
Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 22
Example: Standardization of Titrant Followed by
Analysis of Unknown (6 of 7)
Solution: In 16.17 mL of MnO4− , there are (0.016 17 L) (8.7947 × 10−4 mol/L) =
1.4221 × 10−4 mol MnO4− . This quantity will react with
5 mol C2O24−
Moles of C2O24− = (molMnO −
4 ) = 0.035 553 mmol
2 molMnO4 −
Because there is one oxalate ion for each calcium ion in Ca(C2O4)∙ H2O, there must
have been 0.035 553 mmol of Ca2+ in 5.00 mL of urine:
2+0.035 553 mmol
[Ca ] = = 0.007 111 M
5.00 mL
Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 23
Example: Standardization of Titrant Followed by
Analysis of Unknown (7 of 7)
Test Yourself: In standardization, 10.00 mL of Na2C2O4 solution required 39.17 mL of
KMnO4. Find the molarity of KMnO4. The unknown required 14.44 mL of MnO4− .
Find [Ca2+] in the urine.
Suppose that 0.356 2 g of Na2C2O4 is dissolved in a 250.0-mL volumetric flask.
Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 24
Example: Titration of a Mixture (1 of 3)
A mixture weighing 1.372 g containing only sodium carbonate and sodium
bicarbonate required 29.11 mL of 0.734 4 M HCl for complete titration:
Na2CO3 + 2HCl → 2NaCl(aq) + H2O + CO2
FM105.99
NaHCO3 + HCl → NaCl(aq) + H2O + CO2
FM 84.01
Find the mass of each component of the mixture.
Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 25
Example: Titration of a Mixture (2 of 3)
Solution: Let’s denote grams of Na2CO3 by x and grams of NaHCO3 by 1.372 – x. The moles of each
component must be
xg (1.372 − x) g
Moles of Na2CO3 = Moles of NaHCO3 =
105.99 g/mol 84.01 g/mol
We know that the total number of moles of HCl used was (0.029 11 L)(0.734 4 M) =
0.021 38 mol. From the stoichiometry of the two reactions, we can say that
2(mol Na2CO3) + mol NaHCO3 = 0.021 38
xg (1.372 − x) g
2 + = 0.021 38 x = 0.724 g
105.99 g/mol 84.01 g/mol
The mixture contains 0.724 g of Na2CO3 and 1.372 – 0.724 = 0.648 g of NaHCO3.
Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 26
Example: Titration of a Mixture (3 of 3)
Test Yourself: A 2.000-g mixture containing only K2CO3 (FM 138.20) and KHCO3 (FM
100.11) required 28.10 mL of 1.000 M HCl for complete titration. Find the mass of
each component of the mixture.
Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 27
Section 7-3
Precipitation Titration Curves
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Precipitation Titration Curves
Titration curves show how concentration of reactant varies as titrant is added
• Understand the chemistry that occurs during titration
• Learn how experimental control can influence quality of analytical titration
Sharpness of end point is influenced by:
• Concentration of analyte and titrant
• Size of solubility product (Ksp)
Concentration varies over orders of magnitude so use p function.
pX = − log10[X]
Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 29
Equivalence Point of Precipitation Titration (1 of 2)
Consider the titration of 25.00 mL of 0.100 0 M I− with 0.050 00 M Ag+.
• The equilibrium constant of a titration reaction is large (K = 1 / K sp = 1.2 1016 ).
• Equilibrium lies far to the right; therefore, each aliquot of Ag+ reacts nearly
completely with I−.
At equivalence point there will be a sudden increase in [Ag+] because
there is no I− left to consume the added Ag+.
Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 30
Equivalence Point of Precipitation Titration (2 of 2)
What volume of Ag+ titrant is needed to reach
equivalence point (Ve)? I + Ag → AgI ( s )
− +
• Stoichiometry of the reaction is 1:1, so
(0.025 00 L)(0.100 00 mol I− /L) = (Ve )(0.500 00 mol Ag + /L)
Moles I− Moles Ag +
Ve = 0.050 00 L = 50.00 mL
The titration curve has three distinct zones:
1. Before Ve
2. At Ve
3. After Ve
Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 31
Before the Equivalence Point (1 of 2)
• Suppose 10.00 mL of Ag+ have been added.
• There are more moles of I− than Ag+ at this point, virtually all Ag+ is
“used up” to make AgI(s).
• But a small amount of [Ag+] remains in solution from AgI(s) that
redissolves according to Ksp.
So let’s calculate [Ag+].
Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 32
after 10.00 mL of Ag+
Before the Equivalence Point (2 of 2) has been added
Unprecipitated I−: Moles of I− = original moles of I− − moles of Ag+ added
= (0.025 00 L)(0.100 00 mol/L) − (0.010 00 L)(0.500 00 mol/L)
= 0.002 000 mol I−
Concentration Ag + : [Ag + ] = K sp /[I− ]
[Ag + ] = (8.3 10 −17 ) / (0.057 14) = 1.4 5 10 −17 M Ag + pAg + = 14.84
Same Calculation Streamlined (titration is 1/5 complete)
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Recall Significant Figures
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Example: Using the Streamlined Calculation (1 of 3)
Let’s calculate pAg+ when VAg+ (the volume added from the buret) is
49.00 mL.
Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 35
Example: Using the Streamlined Calculation (2 of 3)
Solution: Because Ve = 50.00 mL, the fraction of I− reacted is 49.00/50.00, and the
fraction remaining is 1.00/50.00. The total volume is 25.00 + 49.00 = 74.00 mL.
− 1.00 25.00 mL −4
[I ] = (0.100 0 M) = 6.76 10 M
50.00 Original 74.00 mL
Fraction concentration Dilution
remaining factor
[Ag+] = Ksp/[I−] = (8.3 × 10−17)/(6.76 × 10−4) = 1.23 × 10−13 M
pAg+ = − log[Ag+] = 12.91
The concentration of Ag+ is negligible compared with the concentration of unreacted I−,
even though the titration is 98% complete.
Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 36
Example: Using the Streamlined Calculation (3 of 3)
Test Yourself: Find pAg+ at 49.10 mL.
Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 37
At the Equivalence Point
• Added exactly enough Ag+ to react with all I−.
• AgI(s) precipitates and some redissolves according to Ksp
equilibrium.
[Ag+][I−] = Ksp
(x)(x) = 8.3 × 10−17
x = 8.3 10 −17 x = 9.1 10 −9 M
pAg + = −log ( x ) pAg + = 8.04
pAg+ is independent of the original concentrations or volumes.
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After the Equivalence Point
• Virtually all Ag+ added before the equivalence point has precipitated.
• Only Ag+ added after the equivalence point remains.
Same Calculation Streamlined
The concentration of Ag in the buret is 0.050 00
M, and 2.00 mL of titrant are being diluted to
(25.00 + 52.00) = 77.00 mL
Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 39
Shape of the Titration Curve
Figure 7-2
Equivalence point is the steepest
point of the curve (maximum slope)
dy
Steepest slope : reaches its greatest value
dx
d 2y
Inflection point : 2 = 0
d x
Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 40
Ksp Affects Titration Equivalence Point
Figure 7-3
Titration curves illustrate effect of Ksp.
• Each curve is calculated for 25.00 mL of
0.100 0 M halide titrated with 0.050 00 M
Ag+
• Equivalence points are marked with
arrows.
At the equivalence point:
• Titration curve is steepest for the least
soluble precipitate
Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 41
Example: Calculating Concentrations During a
Precipitation Titration (1 of 6)
25.00 mL of 0.041 32 M Hg2(NO3)2 were titrated with 0.057 89 M KIO3.
Hg22+ + 2IO3− → Hg2 (IO3 )2 (s)
lodate
For Hg2(IO3)2, Ksp = 1.3 × 10−18. Find [Hg22+ ] in the solution after addition of
(a) 34.00 mL of KIO3; (b) after addition of 36.00 mL of KIO3; and (c) at the
equivalence point.
Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 42
Example: Calculating Concentrations During a
Precipitation Titration (2 of 6)
Solution: The volume of iodate needed to reach the equivalence point is found as
follows:
2 molIO −
Moles of IO3− = 3
(moles of Hg 2+
2 )
1molHg2
2 +
(Ve )(0.057 89 M) = 2(25.00 mL)(0.041 32 M) Ve = 35.69 mL
Moles of IO3− Moles of Hg 22+
Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 43
Example: Calculating Concentrations During a
Precipitation Titration (3 of 6)
Solution: (a) When V = 34.00 mL, the precipitation of Hg22+ is not yet complete.
Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 44
Example: Calculating Concentrations During a
Precipitation Titration (4 of 6)
Solution: (b) When V = 36.00 mL, the precipitation is complete. We have gone (36.00 –
35.69) = 0.31 mL past the equivalence point. The concentration of excess IO3− is
The concentration of Hg22+ in equilibrium with solid Hg2(IO3)2 plus this much I O −
3 is
−18
K sp
1.3 10
[Hg22+ ] = − 2 = −4 2
= 1.5 10 −11
M
[IO3 ] (2.94 10 )
Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 45
Example: Calculating Concentrations During a
Precipitation Titration (5 of 6)
Solution: (c) At the equivalence point, there is exactly enough IO3− to react with all
Hg22+ . We can imagine that all of the ions precipitate and then some Hg2(IO3)2(s)
redissolves, giving two moles of iodate for each mole of mercurous ion:
Hg2 (IO3 )2 (s) Hg22+ + 2IO3−
x 2x
(x)(2 x)2 = K sp x = [Hg22+ ] = 6.9 10 −7 M
Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 46
Example: Calculating Concentrations During a
Precipitation Titration (6 of 6)
Test Yourself: Find [Hg22+ ] at 34.50 and 36.5 mL.
Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 47
Section 7-4
Titration of a Mixture
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Titration of a Mixture (1 of 2)
If a mixture of two ions is titrated, the less soluble precipitate forms first.
• The first precipitation is nearly complete before the second commences, if the
solubilities are sufficiently different.
Consider the addition of AgNO3 to a solution of KI and KCl.
• Ksp(AgI) << Ksp(AgCl) I− + Ag+ → AgI(s); Ksp = 8.3 × 10−17
• AgI precipitates first. Cl− + Ag+ → AgCl (s); Ksp = 1.8 × 10−10
• When precipitation of I− is almost complete, [Ag+] abruptly increases.
• This increase in [Ag+] causes AgCl to begin precipitating.
• When Cl− is consumed another abrupt increase in [Ag+] occurs.
We expect two breaks in the titration curve (Ve for AgI and Ve for AgCl).
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I− + Ag+ → AgI (s); Ksp = 8.3 × 10−17
Titration of a Mixture (2 of 2) Cl− + Ag+ → AgCl (s); Ksp = 1.8 × 10−10
Figure 7-4 Figure 7-5
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Section 7-5
Calculating Titration Curves with
a Spreadsheet
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M+ , Titrant X − , Analyte
+ −
M +X MX(s) (7-9) 0
CM , VM C X0 , VX0
Spreadsheets are a powerful tool and more efficient than hand calculations
The key is sorting out relevant equations.
0
Mass balance for M : CM VM = [M+ ](VM + VX0 ) + molMX(s)
Totalmol Moles of M
(7-10)
of added M Moles of M in precipitate
in solution
Mass balance for X : C X0 VX0 = [X + ](VM + VX0 ) + molMX(s) (7-11)
Totalmol Moles of X
of added X Moles of X in precipitate
in solution
C 0
+ [M+
] − [X −
]
Precipitation of X − with M + : VM = VX0 X0 (7-12)
CM − [M+ ] + [X − ]
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Calculating Titration Curves with Spreadsheets
Figure 7-6
Precipitation of X− with M+:
C 0
+ [M+
] − [X −
]
VM = VX0 X0 (7-12)
CM − [M ] + [X ]
+ −
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[Link]
[Link]
Section 7-6
End-Point Detection
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Volhard Titration
Volhard titration commonly used to measure [Cl−] (can be adapted for
other anions)
• Depends on the formation of a soluble, colored complex at the endpoint
• Back titration and excess Ag+ used to measure Cl−
Ag+ + Cl− → AgCl(s)
• Titration of excess Ag+ with standard KSCN in ~0.5 M HNO3
Ag+ + SCN− → AgSCN(s)
• When excess Ag+ has been consumed, Fe3+ forms a visible red complex
Fe3+ + SCN− → FeSCN2+ Titrations with Ag+ are called
Red complex
argentometric titrations.
Appearance of red color is the end point
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[Link]
Fajans Titration
Figure 7-7
Fajans titration can be applied to many systems
• Depends on adsorption of a colored indicator onto the
precipitate at the end point
• Adsorption indicators are negatively charged.
• When precipitate is formed, e.g., AgCl(s), some of the Cl−
in solution adsorbs on the surface prior to Ve.
• After Ve, excess Ag+ in solution adsorbs, making the
surface of the precipitate positively charged.
• The negatively charged dye adsorbs onto the positively
charged surface and changes color.
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Adsorption Indicators
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Table 7-1 Applications of precipitation titrations (1 of 2)
Species analyzed Notes
Volhard Method
Br − , I− , SCN − , CNO− , AsO3−
4 Precipitate removal unnecessary
Cl− , PO3− − 2− 2− 2− 2−
4 , CN , C2 O4 , CO3 , S , CrO4 Precipitate removal required
BH4− Back titration of Ag + left after reaction with BH4− :
BH4− + 8Ag + + 8OH − → 8Ag 𝑠 + H2 BO− 3 + 5H2 O
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Table 7-1 Applications of precipitation titrations (2 of 2)
Species analyzed Notes
Fajans Method
Cl− , Br − , I − , SCN − , Fe(CN)4−
6 Titration with Ag + ; detection with dyes such as fluorescein,
dichlorofluorescein, eosin, bromophenol blue
Zn2+ Titration with K4Fe(CN)6 to produce K2Zn3[Fe(CN)6]2; end-point
detection with diphenylamine
SO2−
4 Titration with Ba(OH)2 in 50 vol% aqueous methanol using alizarin
red S as indicator
Hg 2+
2 Titration with NaCl to produce Hg2Cl2; end point detected with
bromophenol blue
PO3− 2−
4 , C2 O4 Titration with Pb(CH3CO2)2 to give Pb3(PO4)2 or PbC2O4; end point
detected with dibromofluorescein (PO3− 2−
4 ) or fluorescein (C2 O4 )
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