TITRIMETRIC METHODS OF ANALYSIS Back-titration is a process in which the excess of a

standard solution used to consume an analyte is determined

 based upon measuring the amount of reagent of known by titration with a second standard solution. Back titrations
concentration that is consumed by the analyte. are often required when the rate of reaction between the
analyte and reagent is slow or when the standard solution
Volumetric Titrimetry – involves measuring the volume of lacks stability
a solution of known concentration that is needed to react
essentially and completely with the analyte. Standardization is a process in which the concentration of
a volumetric solution (secondary standard) is determined by
Gravimetric Titrimetry – differs only in that the mass of using it to titrate a known mass of a primary standard or an
the reagent is measured instead of its volume. exactly known volume of another secondary standard
solution.
Coulometric Titrimetry – the reagent is a constant direct
electric current of known magnitude that is directly or The equivalence point is the point in a titration when the
indirectly reacts with the analyte, here, the time required to amount of added standard reagent is exactly equivalent to
complete the electrochemical reaction is measured. the amount of analyte.

General Aspects of Volumetric Titrimetry The end point is the point in a titration when a physical
Titrimetric methods of analysis are capable of rapid and change occurs that is associated with the condition of
convenient analyte determinations with high accuracy and chemical equivalence.
precision. Titrimetric analysis is based on the complete
reaction between the analyte and a reagent, the titrant: The difference in volume or mass between the equivalence
point and the end point is the titration error
aA + tT  products
titration error: Et=Vep-Veq
where A and T represent the analyte and titrant,
respectively, and a and t are the stoichiometric coefficients.
Titrations are often classified by the nature of this titration
reaction: acid-base, redox, precipitation and complexation
reactions are the most common reaction types.

Quantitative determination of the analyte concentration

requires the following:
1. There is a stoichiometric reaction between analyte
and titrant. This reaction should be fast and
complete, and the values of a and t must be known.
2. The concentration of the titrant solution, CT, must
be known accurately. The titrant solution must be
standardized either by preparing it using a primary
standard or, more commonly, titrating it against a
solution prepared with a primary standard.
3. The endpoint volume must be measured accurately
using an appropriate chemical indicator or
instrumental method. If an instrumental method is
used to follow the progress of the titration reaction,
a titration curve may be generated, which allows for Indicators are added to the analyte solution to produce an
the analysis of mixtures and/or the detection of observable physical change (the end point) at or near the
interferences. equivalence point: change in color or appearance or
disappearance of turbidity

Standard solution is a reagent of exactly known Desirable Properties of Standard Solutions

concentration that is used in a titrimetric analysis The ideal standard solution for titrimetric method will:
1. be sufficiently stable so that it is only
Primary standard is an ultrapure compound that serves as necessary to determine its concentration
the reference material for a titrimetric method of analysis. once.
Requirements: 2. react rapidly with the analyte so that the
1. high purity; established methods for time required between the additions of
confirming purity should be available. reagent is minimized.
2. stability towards air 3. react more or less completely with the
3. absence of water of hydration so the analyte so that satisfactory endpoints are
composition of the solid does not realized.
change with variation in humidity 4. undergo a selective reaction with the
4. ready availability at modest cost analyte that can be described by simple
5. reasonable solubility in the titration balanced equation.
medium
6. reasonably large molar mass so that Methods of Establishing the Concentration of Standard
the relative error associated with Solutions
weighing the standard is minimized 1. Direct Method – here, a carefully weighed
quantity of a primary standard is dissolved in a
Secondary standard is a compound whose purity has been suitable solvent and diluted to an exactly
established by chemical analysis and that serves as the known volume in a volumetric flask.
reference material for a titrimetric method of analysis. 2. Standardization – here, the titrant to be
standardized is used to titrate: a.) a weighed
Titration is a process in which a standard reagent is added quantity of primary standard, b.) a weighed
to a solution of an analyte untill the reaction between the quantity of secondary standard, or c.) a
analyte and the reagent is judged to be complete. measured volume of another standard
solution.
Titrations can be classified by the type of reaction. Different equivalent weight = amount of substance that reacts
types of titration reaction include: with or supplies 1 mol of H+ ions in the given reaction

Acid-base titration is based on the neutralization reaction e.g. HCl a = 1 eq/mol → EW =

between the analyte and an acidic or basic titrant. These 36.46 g/eq
most commonly use a pH indicator, a pH meter, or a H2SO4 a = 2 eq/mol → EW =
conductance meter to determine the endpoint. 98.08 g/2 eq = 49.04 g/eq
NaOH a = 1 eq/mol
Redox titration is based on an oxidation-reduction reaction Ba(OH)2 a = 2 eq/mol
between the analyte and titrant. These most commonly use a b. precipitation/complex formation: a = based on the
potentiometer or a redox indicator to determine the number of univalent cation
endpoint. Frequently either the reactants or the titrant have equivalent weight = amount of substance that reacts
a color intense enough that an additional indicator is not with or supplies 1 mol of
needed. univalent cation (1/2 mol of
divalent cation, 1/3 mol of
Complexometric titration is based on the formation of a trivalent cation, and so on)
complex between the analyte and the titrant. The chelating e.g. KCl: K+ and Cl- a = 1
agent EDTA is very commonly used to titrate metal ions in eq/mol
solution. These titrations generally require specialized Ca(NO3)2: Ca2+ and NO3- a = 2
indicators that form weaker complexes with the analyte. A eq/mol
common example is Eriochrome Black T for the titration of Al2(CO3)3 : 2 x Al+3 ; a= 2x 3eq/mol
calcium and magnesium ions.
c. redox reaction: a = total number of electrons gained
A form of titration can also be used to determine the or lost during redox reactions
concentration of a virus or bacterium. The original sample is equivalent weight = amount of substance that directly
diluted (in some fixed ratio, such as 1:1, 1:2, 1:4, 1:8, etc.) or indirectly produces 1 mol of electron
until the last dilution does not give a positive test for the e.g. C2O42- → CO2 a = 2 eq/mol
presence of the virus. This value, the titre, may be based on MnO4- → Mn2+ a = 5 eq/mol
TCID50, EID50, ELD50, LD50 or pfu. This procedure is more
commonly known as an assay. Relationship of Molarity and Normality

VOLUMETRIC CALCULATIONS mol eq

M= ;N= hence,
L L
Ways of Expressing Concentration of Solutions
N M
= � N = M �a
1. Mass percentage eq mol
mass % of component =
mass of component in solution Dilution of Solution
x 100%
total mass of solution
When a solution is diluted:
2. Volume percentage
 the volume is increased by adding more solvent
volume % of component =
 the concentration is decreased, and
volume of component in solution
x 100%  the total amount of solute remains constant
total volume of solution
3. Parts per million, ppm (for very dilute solutions) Dilution Formula: C1V1 = C2V2
ppm component = where C1 ≡ initial concentration
mass of component in solution C2 ≡ final concentration
x 106 = 1mg/kg solution =
total mass of solution V1 ≡ initial volume
1mg/ L solution = 1g/mL V2 ≡ final volume
parts per billion, ppb =
mass of component in solution 9
Sample Problems:
x 10 = μg/L solution
total mass of solution
4. mole fraction,  1. Calculate the molar concentration of ethanol in aqueous
solution that contains 2.30 g of ethanol (46.07 g/mol) in
moles of component in solution
= 3.50 L of solution.
total moles of all component
5. Molality, m (does not vary with temperature)
moles of solute
m= (mol/kg)
kilogram of solvent
6. Molarity, M
moles of solute
M= (mol/L)
liter of solution
2. Calculate the analytical and equilibrium conc. Of the
7. Normality, N
solute species in aq. solution that contains 285 mg of
# of equivalents of solute
N= (eq/L) trichloroacetic acid Cl3CCOOH (163.4 g/mol) in 10.0
liter of solution mL (the acid is 73% ionized in water).
where # of equivalents =
weight of solute
equivalent weight (EW) of solute
MW g
EW = =
a eq
3. Describe the preparation of the following:
# of equivalents a. 2.00 L of 0.108 M BaCl 2 from BaCl22H2O (244.3
a = depends on the
mol solute g/mol)
nature of the solute
when the solute participates in:
a. acids/base reaction: a = number of replaceable H + or
OH- per mole of an acid/base
 b. To what volume should 100. mL of the above solution
be diluted to prepare 1.50 N solution?

b. 500 mL of 0.0740 M Cl – solution from solid

BaCl22H2O

4. A solution is prepared by dissolving 1.26 g AgNO 3

(169.9 g/mol) in a 250 mL volumetric flask and diluting
to volume. a.) Calculate the molarity of the soilver
nitrate solution. b.) How many millimoles AgNO 3 were
dissolved? 10. A solution was prepared by dissolving 15.35 g of
FeSO4(NH4)2SO46H2O (FW 392.14) in sufficient water to
give 2.00 L. Calculate:
a. the molar analytical concentration of
FeSO4(NH4)2SO4
b. the molar concentration of NH4+
c. mmoles of SO42– in 25.00 mL of this solution
5. Calculate the concentration of potassium ions in d. ppm Fe2+
grams per liter after mixing 100 mL of 0.250 M KCl and
200 mL of 0.100 M K2SO4. (Assume volumes are 11. A water sample is 0.00026 M in CaCO 3. Calculate
additive) the concentration in ppm.
12.

6. Given the unbalanced equations: 13.

i. CaO + HCl  CaCl2 + H2O 14.
ii. MnO4– + CN– + H2O  MnO2 (s) + CNO– + OH–
iii. Hg2+ + Cl–  HgCl2 15.
Balance each equations and calculate the equivalent weights 16. Calculate the number of milliliters of nitric acid,
of the following substances in terms of its formula weights density 1.42g/mL, 72.0% HNO3 by weight, that should
when used in the above reaction. be taken to prepare 1.5 liters of a 0.15 M solution.
a. CaO b. HCl
cb. KMnO4 d. KCN
ec. Hg(NO3)2 f. KCl

Quantitative Treatment of Titration Data and

Percent Purity
7. Calculate the normality of the solutions containing To analyze a sample of unknown purity the analyst
the following: weighs accurately a portion of the sample, dissolves it
appropriately, and titrates it with a standard solution. If the
a. 5.300 g/L Na2CO3 (105.99) titration reaction is

a A + t T  products
where a molecules of the analyte, A, react with t molecules
b. 5.267 g/L K2Cr2O7 (294.19) in the reaction:
of the titrant, T, then at the equivalence point
Cr2O72– + 14H+ + 6e–  2Cr3+ + 7H2O

t x mmol A = a x mmol T
a OR
mmol A = x mmol T
8. As a diacidic base, calculate the amount (in grams) t
of Na2CO3 (105.99) present in 100. mL of 0.0400 N meq A = meq T
Na2CO3 solution.
If V and M represents the volume (mL) and molarity
(mmol/mL), respectively, of the titrant, and MWA is the
formula weight of the analyte, then

a
mmol A = x V xM
9. a. Calculate the normality and molarity of a 13.0% t
(by weight) H2SO4 solution with a specific gravity of
1.090. a
mg A = x V x M x MWA
t
The percent by weight of A is
 mg analyte
% A= x 100
mg sample
a
x V (mL ) x M (mmol / mL) x MWA (mg / mmol )
% A= t x 100
weight of sample (mg )

In terms of normality,N of the titrant and equivalent weight,

EWA, of the analyte:
2. Standardization of an acid solution .
meq A = meq T An approximately 0.10 M HCl is prepared by 120 fold dilution
of concentrated HCl. It is standardized by titrating
mg A = V x N x EWA 0.1876 g of dried primary standard sodium carbonate:
mg analyte CO32– + 2H+  H2O + CO2
% A= x 100 The titration required 35.86 mL acid. Calculate the
mg sample molarity and normality of the HCl solution.
V (mL) x N (meq / mL) x EWA (mg / meq )
% A= x 100
weight of sample (mg )

Gravimetric Titrimetry
 Mass of titrant is measured rather than the volume
 For weight titration, an analytical balance and a
solution dispenser are substituted for a buret and its
markings . 3. Standardization with back-titration .
Calculate the normality of NaOH and HCl given the
following data:
1.000 m L of HCl  0.7005 mL NaOH
mass of KHP used = 0.4998 g
Calculations involved:
total volume of NaOH used = 21.00 mL
Weight molarity, Mw = mol /kg sol’n
total volume of HCl used = 1.25 mL
- no. of moles reagent in 1 kg of solution
- no. of mmols solute in 1 g of solution.

Advantages of Weight Titration: (compared to Volume

Molarity)
1. Calibration of glasswares and tedious cleaning to ensure
drainage is avoided.
2. Temperature corrections are unnecessary because weight
molarity does not change with temperature.
3. Weight measurements can be made with considerably
greater precision and accuracy.
4. Standardization of an oxidant.
4. Weight ttitrations are more easily automated.
A solution of KMnO4 is standardized using sodium oxalate
Na2C2O4 as the primary standard
Sample Problem:
5 C2O4 -2 + 2MnO4– + 16H+  2Mn2+ +10CO2 + 8H2O
Titration of 0.824 g of potassium hydrogen phthalate
A sample of sodium oxalate 0.3248g g requires 44.22
(KHP) (FW 204.23) required 38.314 g of NaOH solution to
mL of KMnO4 for titration. Calculate the molarity and
reach the end point detected by phenolphthalein
normality of the KMnO4 solution.
indicator. Find the weight molarity of the NaOH solution.

17. Fifty (50) mL of 0.12 M KMnO 4 is mixed with 50 mL

of 0.080 M Na2C2O4 in a strongly acidic solution. This
reaction occurs:
5 C2O42– + 2MnO4– + 16H+  10CO2 + 2Mn2+ + 8H2O
5. Standardization using an indirect standard. A solution of
Assuming the final volume is 100 mL, calculate a) the
HClO4 was standardized by dissolving 0.3745 g of
molarity of the reagent in excess, and b) the molarity of
primary standard HgO (FW 216.59) in a solution of KBr:
Mn2+.
HgO + 4Br– + H2O  HgBr42– + 2OH–
The liberated OH– required 37.79 mL of the acid to be
neutralized. Calculate the molarity of the HClO4 solution.

PROBLEMS: Treatment of Titration Data

1. Standardization of a base solution.

Titration of 0.8241.000 g of potassium hydrogen phthalate

(KHP) (FW 204.23) required 38.35 mL of NaOH solution to
reach the end point detected by phenolphthalein indicator.
Standardization of an oxidant with back titration. A
Find the molarity and normality of the NaOH solution.
sample of sodium oxalate, Na2C2O4 (134.00), weighing
0.2856 g is dissolved in H2O, sulfuric acid is added and the
solution is titrated at 70oC, requiring 45.12 mL of a KMnO4 Percent Purity
solution. The end point is overrun and back-titration is To analyze a sample of unknown purity the analyst
carried out with 1.74 mL of 0.0516 M of oxalic acid solution. weighs accurately a portion of the sample, dissolves it
Calculate the normality and molarity of the KMnO4 solution. appropriately, and titrates it with a standard solution. If the
The chemical reactions involved are: titration reaction is

C2O42–  CO2 and MnO4–  Mn2+ a A + t T  products

wher amolecules of the analyte, A, react with t molecules of
Aliquot – small amount of sample used for analysis
the titrant, T, then at the equivalence point
6. A sample of pure CaCO3 (FW 100.09) weighing 0.4148 g
is dissolved in 1:1 hydrochloric acid, and the solution is t x mmol A = a x mmol T
diluted to 500.0 mL in a volumetric flask. A 50.00 m L a OR
aliquot is withdrawn with a pipet and placed in an mmol A = x mmol T
Erlenmeyer flask. The solution is titrated with 40.35 mL t
of an EDTA solution using Eriochrome Black T (EBT) meq A = meq T
indicator. Calculate the molarity of the EDTA solution. If V and M represents the volume (mL) and molarity
The reaction in the titration is: (mmol/mL), respectively, of the titrant, and FWA is the
Ca2+ + EDTA  Ca[EDTA]2– formula weight of the analyte, then
The titer (mg Solid/mL solution) of a solution is the
weight(in mg) of a substance that is chemically equivalent to a
mmol A = x V xM
1 mL of the solution. t
a
mg A = x V x M x MWA
t
The percent by weight of A is

mg analyte
% A= x 100
mg sample
7. Calculate a) the Na2CO3 titer in mg/mL of a 0.1200 M
solution of HCl; ( FW Na2CO3 =105.0099 g/mol) Ans. a
x V ( mL) x M (mmol / mL) x MWA ( mg / mmol )
6.359mg/mL
% A= t x 10
b) A standard solution of potassium dichromate K-
weight of sample (mg )
2Cr2O7 contains 5.442 g/L. What is its titer in terms of
milligrams FeO per mL of K2Cr2O7? (FW: K2Cr2O7 In terms of normality,N of the titrant and equivalent weight,
=294.20 g/mol ; FeO =71.85 g/mol) EWA, of the analyte:
6Fe2+ + Cr2O72– + 14 H+2Cr3+ + 6 Fe3+ + 7H2O
meq A = meq T
Ans. 7.974 mg FeO/mL pot. dichromate Fe2+Fe3+;
Cr2O72– Cr3+) mg A = V x N x EWA
mg analyte
% A= x 100
mg sample
c ) the Fe2O3 (FW 159.70) titer of a 0.0200 M solution of
V (mL) x N ( meq / mL) x EWA ( mg / meq)
K2Cr2O7. The reaction is % A= x 100
( 6Fe2+Fe3+; + Cr2O72– + 14 H+2Cr3+) + 6 Fe3+ + weight of sample (mg )
7H2O 10. The organic matter in a 3.776 g sample of a mercuric
Ans. 9.582 mg ferric oxide/mL pot. dichromate ointment is decomposed with HNO3. After dilution, the
Hg2+ is titrated with 21.30 mL of a 0.1144 M solution of
8. Calculate the normality of: NH4SCN. Calculate the percent Hg (FW 200.59) in the
a) the N of )a a solution of KMnO4 which has a Na2C2O4 ointment. The titration involves the formation of a
(FW 134.00) titer of 8.04 mg/mL stable neutral complex, Hg(SCN)2: Hg2+ + 2SCN– 
(5 C2O42– + MnO4– + 16H+ 10 CO2; MnO4–  + Mn2+
Hg(SCN)2
) + 8H2O
Ans. 0.1200 meq/mL pot. permanganate 11. A 1.000 g sample containing NaC2O4 (FW 126.0) is
b) the normality of a solution of NaOH which has a KHP titrated with 40.00 mL of 0.0200 M KMnO4 in acid
(FW 204.23) titer of 20.05 mg/mL. solution. Calculate the percent purity of the sample.
Ans. 0.09817 meq/mL NaOH

9. Exactly 50.00 mL of HCl solution required 29.71 mL of

0.01963 M Ba(OH)2 to reach an end point with
bromocresol green indicator. Calculate the molarity of
the HCl solution.

12. A sample of iron ore weighing 0.6428 g is dissolved in

acid, the iron reduced to Fe2+, and the solution titrated
with 36.30 mL of a 0.1052 N solution of K2Cr2O7.
(Fe2+  Fe3+; Cr2O72–  Cr3+). a) Calculate the
percentage of iron, Fe (FW 55.847) in the sample. b)
Express the percentage as Fe2O3 (FW 159.69).
 34.15 mL of a 0.0566 M solution of I2. (HAsO2 
H3AsO4; I2  I–) Calculate a) the percentage As in the
sample; b) the percentage As2O3.

In the Kjeldahl method for nitrogen determination,,

the element is converted into NH3, which is then distilled into
a known volume of standard acid. There is more than
enough acid to neutralize the NH3, and the excess is titrated
with standard base.

13. The ammonia from a 1.325 g sample of fertilizer is

distilled into 50.00 mL of 0.1015 M H2SO4, and 25.32 mL
of 0.1980 M NaOH is required for back-titration.
Calculate the percentage of nitrogen in the sample.
18. The arsenic in a 1.223 g sample of pesticide was
converted to H3AsO4 by suitable treatment. The acid
was then neutralized, and exactly 40.00 mL of 0.07891
M AgNO3 was added to precipitate the arsenic
quantitatively as Ag3AsO4. The excess Ag+ in th filtrate
and washing from the precipitate was titrated with
11.27 mL of 0.100 M KSCN. Calculate the %As2O3 in the
sample.
14. A 1.047 g sample of canned tuna was analyzed by the Ag+ + SCN–  AgSCN
Kjeldahl method. The liberated NH3 required 24.65 mL of H3AsO4 + 3AgNO3  Ag3AsO4 + 3HNO3
0.1180 M HCl. Calculate the percentage protein in the 16. A 0.4755 g sample containing (NH4)2C2O4 and inert
sample. Assume that the protein factor is 6.25, i.e. % materials was dissolved in H2O and made strongly
protein = % N x 6.25 alkaline with KOH, which converted NH4+ to NH3. The
Ans. 3.892% N, 24.32% protein liberated NH3 was distilled into exactly 50.00 mL of
0.05035 M H2SO4. The excess H2SO4 was back-titrated
with 11.13 mL of 0.1214 M NaOH. Calculate the a)
percent N (FW 14.007) and b) percent (NH4)2C2O4 (FW
124.10) in the sample.

Ans. 10.85%N, 48.07 % ammonium oxalate

19. A 100.0 mL sample of spring water was titrated to

convert any Fe present to Fe2+. Addition of 25.00 mL of
0.002107 M K2Cr2O7 resulted in the reaction: 6 Fe2+ +
Cr2O72– + 14H+  6Fe3+ + 2Cr3+ + 7H2O. The excess
15. Titrimetric analysis – aliquot portions. A sample K2Cr2O7 was back-titrated with 7.47 mL of 0.00979 M
containing arsenic and weighing 3.458 g is dissolved and Fe2+ solution. Calculate the ppm Fe in the sample.
diluted to exactly 250.0 mL in a volumetric flask. A 50.0
mL aliquot is withdrawn with a pipet and titrated with
34.15 mL of a 0.0566 M solution of I2. (HAsO2  H3AsO4;
I2  I–) Calculate a) the percentage As (74.92 g/mol) in
the sample; and b) the percentage As2O3 (197.84
g/mol) in the sample.
17. The CO in a 20.3 L sample of gas was converted to CO2
Ans. 20.94%As, 27.64%As2O3 by passing the gas over iodine pentoxide heated to
150oC
Titirimetric analysis with back-titration . I2O5 (s) + 5CO (g)  5CO2 (g) + I2 (g)
16. A 1.876 g sample containing oxalic acid, H2C2O4 requires The iodine distilled at this temperature and was
38.34 mL of 0.1032 M NaOH for titration. 1.38 mL of collected in an absorber containing 8.25 mLK of
0.0992 M HCl is used in back-titration. Calculate the 0.01101 M Na2S2O3:
percentage of H2C2O4 in the sample. I2 (aq) + 2S2O32– (aq)  2I–(aq) + S4O62–(aq)
The excess Na2S2O3 was back-titrated with 2.16 mL of
Ans. 9.17%H2C2O4 0.009471 I2 solution. Calculate the number of milligrams
of CO (FW 28.01) per liter of sample.

Ans. 0.1721 mg CO/L

20. Exactly 50.00 mL of an HCl solution required 29.71 mL

of 0.01963 M Ba(OH)2 to reach an end point with
bromcresol indicator. Calculate the molarity of the HCl.
17. Titrimetric analysis – aliquot portions. A sample 21.
containing arsenic and weighing 3.458 g is dissolved and
diluted to exactly 250.0 mL in a volumetric flask. A 50.0
mL aliquot is withdrawn with a pipet and titrated with
 23. The organic matter in a 3.776 g sample of a mercuric
22. ointment is decomposed with HNO3. After dilution, the
Hg2+ is titrated with 21.30 mL of a 0.1144 M solution of
NH4SCN. Calculate the percent Hg (FW 200.59) in the
18. Calculate the alkaline strength of the pearl ash (impure ointment. The titration involves the formation of a
potassium carbonate) in terms of percent K2O (94.20 g/mol) stable neutral complex, Hg(SCN)2: Hg2+ + 2SCN– 
from the following data: Hg(SCN)2
Standardization data :
1.000 mL NaOH = 0.01421 g KHC2O4 (128.12 g/mol)
1.000 mL HCl = 0.9356 mL NaOH
Sample analysis data:
Weight sample = 0.4000 g
HCl used = 45.35 mL
NaOH used for back titration = 1.75 mL

19. A sample of vinegar weighing 2.55 g is titrated with A 0.4755 g sample containing (NH4)2C2O4 and inert materials
NaOH. The end point is overrun, and the solution is titrated was dissolved in H2O and made strongly alkaline with KOH,
back with HCl. From the following data, calculate the acidity which converted NH4+ to NH3. The liberated NH3 was distilled
of the vinegar in terms of percentage acetic acid, into exactly 50.00 mL of 0.05035 M H2SO4. The excess H2SO4
CH3COOH(60.05 g/mol): was back-titrated with 11.13 mL of 0.1214 M NaOH.
Standardization data : Calculate the a) percent N (FW 14.007) and b) percent
1.000 mL HCl  0.002500 g Na2CO3 (106.00 g/mol) (NH4)2C2O4 (FW 124.10) in the sample.
1.000 mL NaOH  0.01150 g benzoic acid C6H5COOH
( 122.12 g/mol)
Sample analysis data:
Volume NaOH used = 19.03 mL
Volume HCl used for back titration = 1.50 mL
Ans. 0.04717 M HCl, 0.09416 M NaOH, 4.05% Acetic acid

The CO in a 20.3 L sample of gas was converted to CO2 by

passing the gas over iodine pentoxide heated to 150 oC
20. Titration of 0.2121 g of pure Na2C2O4 (FW 143.00) I2O5 (s) + 5CO (g)  5CO2 (g) + I2 (g)
required 43.31 mL of KMnO4. What is the normality of The iodine distilled at this temperature and was
the solution? collected in an absorber containing 8.25 mLK of 0.01101 M
Na2S2O3:
I2 (aq) + 2S2O32– (aq)  2I–(aq) + S4O62–(aq)
The excess Na2S2O3 was back-titrated with 2.16 mL of
0.009471 I2 solution. Calculate the number of milligrams of
CO
(FW 28.01) per liter of sample.

21. A 0.8040 g sample of an iron ore is dissolved in acid.

The iron is then reduced to Fe2+ and titrated with 47.22
mL of 0.02242 M KMnO4 solution. Calculate the results REVIEW: Acid-Base Equilibria
of this analysis in terms of a) % Fe (FW 55.847) and b)
%Fe3O4 (FW 231.54) Bronsted-Lowry Theory of Acids and Bases
22.
23. Acid: proton donor
24. BBase: proton acceptor
25.
26. Proton Transfer Reactions:
27. – In a B-L acid-base reaction, a proton is transferred
28. from an acid to a base:
29.
30. HX (aq) + A– (aq)  HA (aq) + X– (aq)
B-

bL acid B-L base

A. Strong acids – dissociates completely into ions

B. Weak Bases/Weak Acids HCl + H2 O → H3O+
1. ammonia, NH3 + Cl–
� NH 4+ + OH -
NH 3 + H 2O ��� HClO4 and HCl have same acid strength.
base acid
Since NH3 is a weak base, the reverse reaction can But in diethylether (C2H5)2O solvent,
occur: HClO4 + C2H5 – O – C2H5 →
ClO4– + [C2H5 – OH – C2H5]+
NH 4+ + OH - ���� NH 3 + H 2O HCl + C2H5 – O – C2H5 →
Cl– + [C2H5 – OH – C2H5]+
The reaction is said to be reversible Thus HClO4 is the stronger acid.
NH 3 + H 2O ���� NH 4+ + OH -
base1 acid 2 acid1 base2 THE AUTOIONIZATION OF WATER

– For the reaction above, when NH3 accepts a proton The extent to which water dissociates into ions is shown as:
from H2O, it becomes NH4+ which act as an acid H 2O ���� H + + OH -
– An acid and base that differ only in the and the equilibrium expression in terms of concentrations for
presence/absence of a proton are called conjugate the forward reaction is:
acid-base pairs
– Thus, NH4+ is the conjugate acid of NH3, and NH3 is
the conjugate base of NH4+; H2O is the conjugate K eq =
 H  OH 
+ -

base of H3O+, and H3O+ is the conjugate acid of  H 2O

H2O.
or
The Base-Dissociation Constant, Kb  
K w = H + OH - 
Consider the general reaction: At 25°C, the ionization constant of water, Kw, is very small:
X (-aq ) + H 2O( l ) ���� HX ( aq ) + OH (-aq ) Kw=1.0 x 10–14
The equilibrium constant for this reaction can be written
p-functions
[ HX ][OH - ]
Kb = pH = – log [H+]; pOH = – log [OH–]; pH +
[X -] pOH = pKw; Ka Kb = Kw

2. acetic acid, HC2H3O2, or CH3COOH, or HOAc

Relative Strengths of Conjugate Acid-Base Pairs
For HOAc, the following reaction is also reversible since
it is a weak acid:

HOAc + H 2O ���� OAc - + H 3O +

acid1 base2 base1 acid2

OAc- (acetate) is the conjugate base of HOAc

H3O+ is the conjugate acid of H2O

The Acid-Dissociation Constant, Ka

Consider the general reaction:
HX ( aq ) + H 2O( l ) ���� H 3O(+aq ) + X (-aq )
which we can simplify as:
HX ( aq ) ���� H (+aq ) + X (-aq ) \
and the equilibrium expression for this as
H + ��
� X -�
K a = � �� �
HX

C. Amphiprotic substances – substances which can act

either as an acid or as a base (can either donate protons or
accept protons depending on the environment), an example
of which is water. Practice Exercises:
1. Calculate the pH and pOH of a solution whose H+
As an acid: concentration is 5.0 x 10–7 M.
2. The pH of a solution is 10.70. Calculate the
� NH 4+ + OH -
NH 3 + H 2O ��� concentration of H+ and OH–.
base acid
3. Calculate the pH and pOH of a 0.0500 M solution of HCl.
4. Calculate the pH and pOH of a 0.0500 FM solution of
As a base: HC2H3O2 (Ka = 1.8 x 10–5)
HOAc + H 2O ���� OAc - + H 3O + 5. Calculate the pH of a solution which is 0.0500 M in a
acid base acetic acid and 0.10 M in sodium acetate.
6. Calculate the pH of a solution made my mixing 50 mL of
D. Solvent Effect – leveling effect of water a 0.10 M NH3 and 50 mL 0.040 M HCl. (Kb of NH3 is 1.8
x 10–5)
Since water can act as a weak base, strong acids 7. Calculate the pH of a 0.10 M solution of sodium acetate
tend to have same strength in water Challenge Problems:
8. Calculate the concentration of all the species in a 0.100
HClO4 + H2 O → H3O+ F H2X (Ka1=1.0 x 10–3; Ka2 = 1.0 x 10–7)
+ ClO4–
9. Calculate the concentration of all the species in a 0.100
F Na2X A. Titration of a strong acid with a strong base
10. Derive an expression for the pH of a 0.100 M NaHX (HX– To derive the titration curve for a solution of strong acid
is the conjugate base of the diprotic acid H2X) with a strong base, three types of pH calculations are
ACID-BASE TITRATIONS required:
1. preequivalence
Theory of Neutralization Titrations 2. equivalence
Standard solutions of strong acids and bases are used 3. postequivalence
extensively for determining analytes that are themselves
acids or bases or analytes that can be converted to such At the preequivalence point, the solution consists of the
species by chemical treatment. excess acid, and the hydronium ion concentration is derived
directly from the concentration of the excess acid
Solutions and Indicators for Acid/Base Titrations
The standard solutions employed in the neutralization At equivalence point, the hydronium ion and hydroxide
titrations are strong acids (SA) or strong bases (SB) because ion are present in equal concentrations, and the hydronium
these substances react more completely with an analyte than ion concentration is derived directly from the ion-product
do their weaker counterparts and thus yield sharper end constant of water.
points.
At the postequivalence point, the solution consist of the
Titration Curves excess base, and the hydronium ion concentration is derived
An end point is an observable physical change that occurs at directly from the concentration of the excess base and the
or near the equivalence point. Two most widely used end ion-product constant of water
points involve:
1. a change in the color due to the reagent, the Derive a curve for the titration of 50.00 mL of 0.0500 M HCl
analyte, or an indicator. with 0.1000 M NaOH by determining its pH at
2. a change in the potential of an electrode that a) initial point (0.00 mL of titrant)
responds to the concentration of the reagent or the
analyte.

Titration curves consist of a plot of reagent volume as the

horizontal axis and some function of the analyte or reagent
concentration as the vertical axis.

Types of Titration Curves

Two general types of titration curves are encountered in
titrimetric methods.
b) after addition of 10.00 mL of NaOH
1. Sigmoidal curve – important observations are confined
to a small region (typically ± 0.1 to ±0.5 ml)
surrounding the equivalence point.

2. Linear-segment curve – measurements are made on

both sides of, but well away from the equivalence point.
Measurements near equivalence point are avoided. The
vertical axis is an instrument reading that is directly
proportional to the concentration of the analyte or
reagent.
c) equivalence point
 The sigmoidal type offers the advantages of speed and
convenience.

 The linear-segment type is advantageous for reactions

that are complete only in the presence of a goodly
excess of the reagent or analyte.

The standard reagents used in acid/base titrations are always

strong acids or strong bases because these substances react
more completely than weak acids/bases. Most commonly
d) after addition of 25.10 mL NaOH
used are HCl, HClO4, H2SO4, NaOH, and KOH.

Titration Curves for Strong Acid and Strong Base

The hydronium ion in an aqueous solution of a strong acid
has two sources:
1. the reaction of the acid with water
2. the dissociation of water.

In most dilute solutions, the contribution from the strong

acid exceeds the solvent.

Ex. For a solution of 1 x 10-6 M HCl

[H3O+] = CHCl + [OH-] = CHCl

Likewise for a strong base, NaOH

[OH-] = CNaOH + [H3O+] = CNaOH

Challenge Problem: Calculate the pH of a 1.0 x 10–8 M HCl

solution.
 Titration curve for the titration of 50.00 mL of 0.100 M HCl with
50.00 mL of 0.100 M NaOH
Titration curve for the titration of 50.00 mL of 0.100 M NaOH with
50.00 mL of 0.100 M HCl
B. Titration of a strong base with a strong Acid
Titration curves for strong bases are derived in the same way
for the strong acids.
Exercises:
Calculate the pH during the titration of 50.00 mL of 0.0500 M 1. Titration Curve for the titration of NaOH with HCl. A.)
NaOH with 0.1000 M HCl after the addition of the following 50.00 mL of 0.0500 M NaOH with 0.1000 M HCl, B.)
volumes of titrant: 50.00 mL of 0.00500 M HCl with 0.01000 M NaOH.
a) 0.00 mL 2. Titration Curve for the titration of NaOH with HCl. A.)
50.00 mL of 0.0500 M NaOH with 0.1000 M HCl, B.)
50.00 mL of 0.000500 M NaOH with 0.001000 M NaOH

BUFFER SOLUTIONS
When a weak acid is titrated with a strong base or a weak
base with a strong acid, a buffer solution consisting of a
conjugate acid/base pair is formed.

A buffer solution is a solution of a conjugate acid/base pair

b) 24.50 mL (weak acid or base) that resists changes in the pH (needed
to maintain the pH of the solution).

Henderson-Hasselbalch Equation

[acid ]
pH = pK a - log
[conj base]
[base]
pOH = pK b - log
c) 25.00 mL [conj acid ]

Calculation of the pH of Buffer Solutions

1. Weak Acid /Conjugate Base Buffers. What is the pH of
the solution that is 0.400 M in formic acid and 1.00 M in
sodium formate. Ka = 1.80 x 10-4

d) 25.50 mL

2. Weak Base/ Conjugate Acid Buffers . Calculate the pH of

the solution that is 0.200 M NH3 and 0.300 M NH4Cl. Kb
= 1.80 x 10-5.

Properties of Buffer Solutions

The Effect of Dilution

The pH of a buffer solution remains essentially independent
of dilution until the concentration of the species it contains is
decreased to the point where approximations become
invalid.
The Effect of Added Acids and Bases
b) after addition of 10.00 mL
Calculate the pH change that takes place when a 100-mL
portion of (a) 0.0500 M NaOH and (b) 0.0500 M HCl is added
to 4.00 mL of the buffer solution containing 0.200 M NH3
and 0.300 M NH4Cl.

c) at equivalence point

Buffer Capacity – defined as the number of moles of a strong

acid or a strong base that causes 1.00 L of the d) after addition of 50.10 mL
buffer to undergo a 1.00-unit change in the pH. The
capacity of the buffer depends not only on the total
concentration of its components but also on their
concentration ratio. Buffer capacity falls off
moderately rapidly as the concentration of the acid
to conjugate base becomes larger or smaller than
unity.

The maximum buffering effect (almost constant pH is

obtained):
a)acid to salt ratio is unity b) base to salt ratio is unity

[ HA] [ B]
=1 =1
[ A- ] [ BH + ]

[ HA] = [ A- ] [ B] = [ BH + ]

Effective buffer
[H+] = Ka pH = pKa
[HA] = [A–]
[OH–] = Kb pOH = pKb
Titration curve for the titration of weak acid with strong base
[B] = [BH+]
D. Titration curves of weak bases with a strong acids
Preparation of Buffers
The derivation of a curve for the titration of weak base is
A buffer solution of any desired pH can be prepared by
similar to that of the weak acid
combining calculated quantities of a suitable conjugate
acid/base pair. Because of some uncertainties, the pH values
Calculate the pH for the titration of 50.00 mL of 0.051000 M
of buffers prepared differ from the predicted values so
NaCN with 0.1000 M HCl after addition of the following
buffers are prepared by making up the solution of
volumes of titrant. The reaction is
approximately the desired pH, and then adjust the pH by
CN– + H3O+  HCN + H2O
adding acid or conjugate base until the required pH is
Kb for CN- = 1.61x10-5
indicated by the pH meter.
a) 0.00 (solution of the weak base)
at the initial point:

C. Titration curves of weak acids with strong bases

Four different types of calculations are needed to derive the
titration curve for weak acids:
a) at the beginning (solution of weak acid)
b) after various increments of the titrant have been b) 10.00 (buffer solution of the weak base and
added (buffer solution of the weak acid and its conjugate acid)
conjugate base)
c) at the equivalence point (solution of the conjugate
base)
d) beyond the equivalence point (solution of the
excess base titrant)

Derive a curve for the titration of 50.00 mL of 0.1000 M

HOAc (Ka = 1.8 x10–5) with 0.1000 M NaOH. Find the pH
a) at initial point

c) 25.00 mL ( buffer solution of wb and conj acid)

 cd) 250.00 (solution of the conjugate acid HCN)

e) 260.00 mL added(solution of the excess acid titrant)

Titration curve for HCl and NaOH: A: 50.00 mL of 0.0500 F HCl with
0.100 F NaOH, B: 50.00 mL of 0.000500 F HCl with 0.00100 F
NaOH

The more concentrated solutions of analyte and

titrant (A) has a steeper slope at the equivalence point
region than the less concentrated solutions of analyte and
titrant (B). As a consequence A can use any of the three
indicators and will still give a sharp end point. B can use only
bromthymol blue for a sharp end point. The other two
indicators will change from acid to base color after addition
of about 5 mL of titrant in the case of bromocresol green
and about 2.5 mL in the case of phenolphthalein. Ideally,
the indicator should change color within one drop from the
equivalence point.
Effect of Reaction Completeness on Titration Curves

The reaction completeness is determined by the value of Ka

or Kb. As the value of K decreases, acid strength or base
strength decreases and the slope of the curve at the
Titration curve for the titration of weak acid with strong base equivalence point region becomes less steep resulting to a
limited choice of indicator.
The titration of a weak acid with a weak base
or of a weak base with a weak acid is not feasible since
the reaction does not proceed to completion, hence the end
point is not sharp and there is no suitable indicator that can
be used in the titration.

For the reaction between HOAc (Ka = 1.8 x 10 –5) and NH3
(Kb = 1.8 x 10–5)
� NH 4+ + OAc -
HOAc + NH 3 ��
� NH 4+ ��
OAc - � H 3O + �
�x � OH - �
��
K = � �� � � �
 HOAc   NH 3  ��
+
H 3O � ��
-
OH �
� �

NH 4+ ��
� OH - � �
H 3O + �OAc - �
�� 1 K K
= � �� �x � � �x = a b
 3
NH  HOAc  � +
�
H 3O ��
� � -
�
OH � K w Effect of acid strength on titration curves: Each curve represents
the titration of 50.00 mL of 0.1000 M acid with 0.1000 M NaOH.

K=
( 1.8 x10 ) ( 1.8 x10 ) = 3.24 x10
-5 -5
3

( 1.0 x10 ) -14

Since K = 3.24 x 103 << 107, then the reaction does not
proceed to completion and the titration is not feasible.

Effect of Concentration on Titration Curves

The greater the concentration of analyte and titrant,

the steeper the slope at the equivalence point region and
hence, the sharper the end point.

Effect of base strength on titration curves: Each curve represents

the titration of 50.0 mL of 0.1000 M base with 0.1000 M HCl.
 - colorless in moderately acidic solutions and exhibit a
Acid-Base Indicators variety of colors in alkaline media but fade slowly in
An acid/base indicator is a weak organic acid or a weak strong alkaline solutions.
organic base whose undissociated form differs in color from - The best-known phthalein indicator is phenolphthalein
its conjugate base or its conjugate acid form. indicator.

Example: The behavior of the acid-type indicator, HIn 2. Sulfonphthalein indicators

- mostly exhibit two useful color-change ranges – one
HIn + H2O ↔ In– + H3O+ in acidic solutions and the other in neutral or
and the acid dissociation constant is moderately basic media.
[ H 3O + ][ In - ] - the basic color shows good stability toward strong
Ka = alkali. The simplest sulfonphthalein indicator is
[ HIn] phenolsulfonphthalein known as phenol red.
In the logarithmic form this becomes
3. Azo indicators
[ HIn]
pH = pK a - log - most exhibit a color change from red to yellow with
[ In - ] increasing basicity; transition ranges are generally on
Suppose that the HIn molecule is red in color and the In – acidic side of neutrality.
molecule is yellow. Both forms are present, of course, in a - The most commonly encountered examples are methyl
solution of the indicator and their relative concentrations orange and methyl red.
depend on the pH. The color that the human eye detects
depends upon the relative amounts of the two forms. Titration Errors with Acid/Base Indicators
Two types of titration errors are encountered in
neutralization titrations
1) systematic errors that occurs when the pH at which
the indicator changes color differs from the pH at
At very acidic pH  Hin predominates and the solution is chemical equivalence.
red; At very basic pH  In– predominates and the 2) random error that originates from the limited ability
solution is yellow of the eye to distinguish reproducibly the
intermediate color of the titration.
The average indicator Hin exhibits its full acid color (red)
when Variables that influence the behavior of indicators
1) Temperature
[ HIn] 10 2) Ionic strength of the medium
�
[ In - ] 1 3) Presence of organic solvents and colloidal particles.
and its full base color (yellow) when
Titration Curves for Complex Acid/Base Systems
[ HIn] 1 Complex systems are defined as solutions made up of:
�
[ In - ] 10 1) Two acids or two bases of different strengths
Substituting this in the above equation 2) An acid or a base that has two or more acidic or
Acid color (yellow): pHy = pKa + log 10/1 = pKa + 1 basic functional groups
Base color (red): pHr = pKa + log 1/10 = pKa – 1 3) An amphiprotic substance which is capable of
pH = pHy – pHr = (pKa + 1) – (pKa – 1) = 2 acting both as an acid and a base.

Thus, the minimum change in pH, pH, required to cause a

Titration Curves for Polyfunctional Acids
detectable color change from red to yellow is 2 pH units.
- multiple end points observed
Indicator range = pKa ± 1
- for titration step to be distinct, Ka1/Ka2 > 103

Example: Derive curve for the titration of 25.00 mL of

0.1000 M maleic acid (H2M) with 0.1000 M NaOH (Ka1 = 1.3
x 10–2; Ka2=5.9x10–7)

Ka1/Ka2 = 2 x 10 4  titration is feasible (2

equivalence points)

a. initial pH – consider only first dissociation of the acid

Some Important Acid/Base Indicators
Common Name Transition pKa Color � H 3O + + HM -
H 2 M + H 2O ��
Range, pH Change
1.2 – 2.8 1.65 R–Y
Thymol blue 2
8.0 – 9.6 8.90 Y–B H 3O + �
�
� �HM - �
�
� � �
�H 3O + �
�
Methyl yellow 2.9 – 4.0 R–Y K a1 = =
Methyl orange 3.1 – 4.4 3.46 R–O  H2M   H2M 
Bromocresol green 3.8 – 5.4 4.66 Y–B and the H+ concentration is solved by quadratic
Methyl red 4.2 – 6.3 5.00 R– Y equation.
Bromocresol purple 5.2 – 6.8 6.12 Y– P
Bromothymol blue 6.2 – 7.6 7.10 Y–B b. before the first equivalence point – simple buffer
Phenol red 6.8 – 8.4 7.81 Y– R solution consisting of weak acid H2M and conjugate
Cresol purple 7.6 – 9.2 Y–P base HM–
Phenolphthalein
Thymolphthalein
8.3 – 10.0
9.3 – 10.5
C–R
C–B pH = pK a1 - log
 H2M 
Alizarin yellow GG 10 – 12 C–Y HM - �
�
� �
COMMON TYPES OF ACID-BASE INDICATORS
c. first equivalence point – solution of salt of HM–
1. Phthalein indicators
 Procedure is straightforward and readily adapted for routine
+
HM - �
Ka2 �
� �+ K w analysis.
�
� �=
H 3O �
HM - �
�
1+ � � Sulfur – determined by burning the sample in a stream of
K a1 oxygen. The sulfur dioxide formed during oxidation is
collected by distillation into a dilute solution of hydrogen
d. after first equivalence point but before the second peroxide. The sulfuric acid is the titrated with a standard
equivalence point – second buffer solution consisting of base.
HM– and M2–; pH is calculated using second Ka (Ka2)
HM - �
�
� �
2. Determination of Inorganic Substances
pH = pK a 2 - log 2-
 numerous inorganic species can be determined; to
�
�M � � name a few are ammonium salts, nitrates and nitrites,
-
carbonates and + H 3O + mixtures.
OHcarbonate �� � 2 H 2O
e. second equivalence point – solution of salt of M 2–

Kw � HM - �
��OH - � Ammonium Salts – determined by the conversion of
K b ( M 2- ) = =� �
2-
� ammonia with strong CO32-base +
+ H 3Ofollowed
�� � HCO -
3 + H 2O
by distillation. The
Ka2 �
�M � � ammonia is collected and titrated as in the Kjeldahl method.
Nitrates and Nitrites – here, ions are first reduced to
f. pH beyond second equivalence point – excess OH–
ammonium ion by Devarda’s alloy, and introduced into a
phenolphthalein
strongly(pHalkaline
= 8.0 solution
– 9.6) of the sample in a Kjeldahl flask.
V
The ammonia is then distilled and titrated.
������ 1
p HCO - + H O + ��
� H CO3 + H 2O
sol'n of NaOH Carbonates and Carbonate Mixtures – here,3 solution
3
contains2
H sodium carbonate, sodium hydrogen carbonate, and sodium
H hydroxide, either aloneV or mixed. The analysis of this
H 2
mixture requires��������
two titrations: �
sol'n of Na2A H 1. with alkaline-range indicator (phenolphthalein)
methyl orange
H 2. with an acid-range(pHindicator
= 3.1 – (bromocresol green
or methyl
V red) 4.4)
���������������
�mo
The composition of the solution can then be deduced from
mLacid
buffer sol'n of HA– and A2– the relative volumes of of HCl
needed to titrate equal volumes
of the sample. Once the composition of the solution has
been established, the volume data can then be used to
determine the concentration of each component in the
sol'n of NaHA sample.

3. Determination of the organic functional groups

buffer sol’n of H2A and HA–  provides direct and indirect determination of several
organic functional groups; example are

carboxylic and sulfonic acid groups – neutralization titrations

are employed to determine the equivalent weight of the
purified organic acids. A base-range indicator such as
Titration of a diprotic acid, H2A with NaOH phenolphthalein is required.

amine groups – Aliphatic amines are titrated with a solution

APPLICATIONS OF NEUTRALIZATION TITRATIONS of a strong acid. Many amines are titrated in nonaqueous
solvents which enhance their basicity.
Reagents for Neutralization Titrations
1. Standard Acid Solutions ester groups – determined by saponification using a
 prepared by diluting an approximate volume of standard base and the excess is titrated with a standard
concentrated reagent, commonly used is HCl. acid.
 standardized against weighed quantities of sodium
carbonate, and other primary standards [TRIS or hydroxyl groups – determined by esterification which
THAM (tris-(hydroxymethyl)aminomethane). produces acetic acid. The acetic acid is then titrated with a
standard solution of alcoholic sodium or potassium
2. Standard Base Solutions hydroxide.
 sodium hydroxide is the most commonly prepared
standard base solution; KOH and Ba(OH)2 are also carbonyl groups – determined with a solution of
encountered. hydroxylamine hydrochloride. In the process, HCl is liberated
 standardized using weak organic acids, most and is titrated with a base.
commonly used is potassium hydrogen phthalate
(KHP). 4. Determination of Salts
 The total salt content of a solution can be accurately
and readily determined by an acid/base titration. The
Typical Applications salt is converted to an equivalent amount of acid or a
1. Elemental Analysis base by passage through a column packed with an
 elements susceptible to this type of analysis are ion-exchange resin.
nonmetallic and include carbon, nitrogen, chlorine,
bromine, and fluorine.
DOUBLE INDICATOR TITRATIONS
Nitrogen – determined using the most common method - determination of the proportions of the components of
known as Kjeldahl method, which is based on a certain mixtures by observing two end points in a single
neutralization titration. Here, the sample is decomposed in titrations.
concentrated acid to convert the nitrogen to ammonia ion.
The liberated ammonia is distilled, collected in an acidic CO32– + H+ ↔ HCO3– pH = ~9
solution, and determined by a neutralization titration. phenolphthalein
 HCO3– + H+ ↔ H2O + CO2 pH = ~4 Sample Problems:
methyl orange/ bromcresol green 1. A solution contains NaHCO3, Na2CO3, and NaOH either
alone or in permissible combination. Titration of 50.00
– it is obvious from the molar relationships of these two mL portion to a phenolphthalein end point requires 22.1
equations that if a certain volume of acid is required to mL of 0.100 M HCl. A second 50.00 mL aliquot requires
convert a given weight of Na2CO3 into NaHCO3, and 48.4 mL of HCl when titrated to a bromocresol green
additional equal volume of the same acid will be required to end point. Deduce the composition and calculate the
complete the reaction. molar solute concentrations of each component in the
original solution. What are the concentrations in mg/mL
of the components of the mixture?

2. A 1.200 g solid sample possibly containing NaHCO 3,

Na2CO3, and NaOH, is dissolved and titrated with 0.1000
M HCl with phenolphthalein as indicator, requiring 22.1
mL of 0.100 M HCl. Another 1.200 g sample requires
48.4 mL of the HCl when titrated to a bromocresol
green end point.
a) Deduce the composition
b) Calculate the percentage of each component

Titration curve for carbonate mixtures titrated with HCl

3. A 0.6234 g sample that might contain
V1 – volume of titrant (HCl) used from the start to NaOH, Na2CO3, NaHCO3, or a permissible mixture of the
phenolphthalein end point bases is titrated with 0.1062 F HCl by the double
V2 – volume of titrant (HCl) used from phenolphthalein end indicator method. It is found that 40.38 mL of the acid
point to methyl orange/bromcresol green end point are required to reach the phenolphthalein end point.
Methyl orange is then added to the solution and the
Vph – volume of titrant (HCl) used from the start to titration continued using an additional 12.83 mL of the
phenolphthalein end point acid. Identify the composition and calculate the
Vmo – volume of titrant (HCl) used from the start to methyl percentage of each in the sample.
orange/bromcresol green end point
4. Given the following volumes of 0.1000 M HCl, deduce
V1 = Vph the composition of the mixture and calculate the
V1 + V2 = Vmo percentage of each component.
V2 = Vmo – Vph Mass of sample: 1.500 g
Composition: Na2CO3, NaHCO3, NaOH, alone or in any
compatible combination with inert materials

Vph, mL Vmo, mL
a. student SA 20.05 46.10
b. SSB 13.00 29.00
c. SSC 32.00 45.00
d. SSD 15.00 15.00
e. SSE 0.00 15.00

Substance mmol of substance

present present (M =
molarity of acid)
NaOH V1>0; Vph > 0; MV1
V2=0 Vmo =
Vph
Na2CO3 V1 = V2 Vph > 0; MV2
Vmo =
2Vph
NaHCO3 V1=0; Vph=0; MV2
V2>0 Vmo > 0
NaOH V1 > V2 Vph > ½ NaOH: M(V1 – V2)
and >0 Vmo > 0 Na2CO3: MV2
Na2CO3
NaHCO3 V2 > V1 ½ Vmo NaHCO3: M(V2 –
and >0 >Vph > V1)
Na2CO3 0 Na2CO3: MV1