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ANALYTICAL CHEMISTRY
Analytical Chemistry
Branch of Chemistry that deals with the analysis, identification, separation and
composition of matter
Involves methods used to identify the substances that are present in a sample
(qualitative analysis) and the exact amount of the identified substances
(quantitative analysis)
Crystalline – particles with size ranging from 100 microns or greater; these
particles settle readily and easily filtered
Particle size is usually affected by temperature, concentration of reactants,
solubility of precipitate and mixing rate
b. Appearance. Precipitates may appear to be colloidal (S) , curdy (AgCl), fine
crystal (BaSO4), coarse crystal (PbCl2) or gelatinous (Al(OH)3)
c. Relative supersaturation (von Weimarn ratio)
Q S
relative supersatur ation
S
where Q = concentration of the solute as precipitation begins and S = solubility
of the precipitate
In order to obtain low relative supersaturation and form a crystalline
precipitate, Q must be minimized and S must be maximized. The following
methods are done to accomplish such conditions:
increase the temperature during precipitation (to maximize S)
precipitate from dilute solution (to minimize Q)
slow addition of precipitating agent with stirring (to minimize Q)
2. Mechanism of precipitation
Precipitation is assumed to occur in two ways:
a. Nucleation
Prevails at high relative supersaturation
Results in the formation of large number of small particles
b. Particle growth
Prevails at low relative supersaturation
Results in the formation of small number of large particles
3. Colloidal precipitates
a. Electrical nature of colloidal suspensions
Suspensions, which are stable since these particles are either positively or
negatively charged, hence repel each other
By heating, stirring and addition of electrolyte causes this suspension to
combine together and form a readily filterable solid
This process of converting a colloidal suspension into a readily filterable
solid is called coagulation or agglomeration
b. Adsorption of colloids
Ions are attached directly to the NO3–
NO – NO3–
solid surface and comprise the 3
Primary
primary adsorption layer Ag+ + NO3– Adsorption
– Ag H+ Layer
The charge of this layer is NO3–
NO3
H+ Ag+ NO3–
dependent on the charge of the Ag+ (AgCl)
Ag+
NO – NO3–
ion present in excess 3
Ag+
n
Ag+
A charged primary adsorption NO3– Ag+ +
H+ NO3–
– Ag
layer attracts excess oppositely NO 3 Counter
NO3– Ag+ Ion
charged ions to form a secondary H+ – Layer
NO 3
layer or counter-ion layer Ag+ NO –
3
These ions, held by electrostatic
forces have higher mobility compared to the ions in the primary layer
The two layers, which constitute an electrical double layer, prevent other
particles to come close thus inhibits the formation of larger aggregates
Chemical and Physical Principles Analytical Chemistry
E. Acid-Base Titration
1. Theories of acids and bases
Theories Acid Base
substances that substances that
Arrhenius theory dissociate in aqueous dissociate in aqueous
Svante August Arrhenius (1859-1927)
solution to form aH3O+ solution to form bHO–
Brønsted-Lowry theory
Johannes Nicolaus Brønsted (1879-1947) proton donor proton acceptor
Thomas Martin Lowry (1874-1936)
4. Calculation of pH
At 25C, the ion product constant for water, KW is equal to 1.00 10–14
At this temperature… pK W pH pOH 14
For a dilute solution at 25C in which the contribution of water to the amount
of H3O+ and HO– in solution and the correction due to activity coefficients are
negligible, the following formulas can be used to calculate the pH:
a. Strong acids (SA) and strong bases (SB)
HA + H2O H3O+(aq) + A–(aq) (SA): pH logMSA
MOH M+(aq) + HO–(aq) (SB): pH 14 logMSB
b. Weak acids (WA) and weak bases (WB)
HA + H2O H3O+(aq) + A–(aq) (WA): pH 12 logK a M WA
B + H2O BH+(aq) + HO–(aq) (WB): pH 14 12 logK b M WB
c. Hydrolysis of salts
As a general rule, salts coming weak acids or weak bases hydrolyze in water,
that is, only the strong conjugate hydrolyzes in water
Acidic salt (AS) is formed from the reaction of a strong acid and weak base
HCl(aq) + NH3(aq) NH4+(aq) + Cl–1(aq)
SA WB SCA WCB
Since only the strong conjugate hydrolyzes in water…
NH4+(aq) + H2O NH3(g) + H3O+(aq)
K [NH 3 ][H 3O ] M
Kh W
(AS): pH 7 12 log AS
Kb [NH 4 ] Kb
Basic salt (BS) is formed from the reaction of a strong base and weak acid
NaOH(aq) + HCN(aq) Na+(aq) + CN–1(aq) + H2O
SB WA WCA SCB
Since only the strong conjugate hydrolyzes in water…
CN–1(aq) + H2O HCN(g) + HO– 1(aq)
K [HCN][HO 1 ] M
Kh W 1
(BS): pH 7 12 log BS
Ka [CN ] Ka
Neutral salt (NS) is formed from the reaction of a strong base and strong acid
Salts from weak acid and weak base (WAB) will have the following
hydrolytic equilibrium expressed by the equation
NH4+(aq) + CN–1(aq) + H2O NH4OH + HCN
KW [HCN][NH 4 OH] K K
Kh 1
(WAB): pH 12 log W a
K a K b [CN ][NH 4 ][H 2 O] Kb
–1 –2
Amphoteric salts (HA or HA )ionize as a weak acid and also a Brønsted
base that hydrolyzes
H3A + H2O H3 O + + H2A–1 Ka1
–1
H2A + H2O H3 O +
+ HA–2 Ka2
HA–2 + H2O H 3 O +
+ A–3
Ka3
K K K a1K a2 [H 2 A ]
1
pH of H 2 A 1 12 log W a1 2 logK a1K a2
1
1
K a1 [H 2 A ]
K K K a2 K a3 [HA ]
2
pH of HA 2 12 log W a2 2 logK a2 K a3
1
2
K a2 [HA ]
Chemical and Physical Principles Analytical Chemistry
To account for the contribution of water to either H3O+ or HO–1 in solution, use the
following scheme:
weak acid (WA)
pH logx
strong base (SB) acidic salt (AS)
KA WA
K
WB
K B
x 2 Mx K W 0 x 2 Kx MK 0 K
W B /K AS
K W /K A BS
pH 14 logx weak base (WB)
strong acid (SA)
basic salt (BS)
Another method requires two duplicate samples. One sample is treated with
phenolphthalein and the other with methyl red. Volumes of titrant required to
reach the phenolphthalein and methyl red endpoints are recorded as V 0-Ph and
V0-MR, respectively.
m-Cresol purple can also be used to detect phenolphthalein alkalinity (P)
while bromocresol green or methyl orange for the total alkalinity (T)
Table 10. Alkalinity relationships
Result from titration NaOH Na2CO3 NaHCO3
V0-Ph > VPh-MR V0-Ph – VPh-MR 2VPh-MR 0
V0-Ph < VPh-MR 0 2V0-Ph VPh-MR – V0-Ph
V0-Ph = VPh-MR 0 2V0-Ph = 2VPh-MR 0
V0-Ph 0 ; VPh-MR > 0 0 0 VPh-MR
V0-Ph > 0 ; VPh-MR 0 V0-Ph 0 0
Note: If analysis involves measurement of volume due to total alkalinity (V0-MR), use the
conversion: VPh-MR = V0-MR – V0-Ph
The following relationship can be summarized using the following diagram:
NaOH Na2CO3
CO2 CO2
Defined as the mass (mg) of KOH required to saponify one gram of fat or oil
Can be used to determine the approximate molar mass of fat or oil
The sample is refluxed with ethanolic KOH and the resulting solution is
titrated with standard HCl
mL
(Vblank Vwith
mL
samplel )(M HCl )(56.10)
Sap Value
gram of fat or oil
168,300
Molar Mass of Fat or Oil
Sap Value
Chemical and Physical Principles Analytical Chemistry
F. Precipitation Titration
1. Important terminologies
Saturated solution – solution that contains the maximum amount of solute
dissolved in a given amount solvent at a specific temperature
Solubility – the maximum amount of solute dissolved in a given solvent at a
specific temperature
Solutions that contain dissolved solute less than the maximum are called
unsaturated while those that contain dissolved solute more than the maximum
are called supersaturated solutions
2. Solubility rules for ionic compounds in water at 25C
Soluble compounds Insoluble compounds
All nitrates, bicarbonates, chlorates All carbonates, phosphates, chromates
and compounds containing alkali and sulfides except that of alkali metal
metal ions and ammonium ion. ions and ammonium ion
All halides except that of Ag+, Hg22+
and Pb2+ All hydroxides except that of alkali
All sulfates except that of Ag+, Ca++, metal ions and Ba++
Sr++, Ba++ and Pb++
3. Solubility product constant (KSP)
Consider an aqueous saturated solution of a sparingly soluble salt represented by
the equation:
AxBy (s) x A+y (aq) + y B–x(aq)
The equilibrium constant for this reaction would be:
[A y (aq) ] x [B x (aq) ] y
K eq
[A x B y(s) ]
However the concentration of the solid AxBy in the solution will be constant (the
ratio of the number moles of AxBy and the volume of the solid is constant). Thus,
K SP K eq [A x B y(s) ] [A y (aq) ] x [B x (aq) ] y
Table 11. Solubility product constants at 25C
COMPOUND KSP COMPOUND KSP
AgCl 1.82 10–10 Mg(OH)2 7.10 10–12
AgBr 5.00 10–13 Ca(OH)2 6.50 10–6
AgI 8.30 10–7 PbCl2 1.70 10–5
BaCO3 5.00 10–9 PbI2 7.90 10–9
Ba(IO3)2 1.57 10–9 Hg2Cl2 1.20 10–18
Al(OH)3 3.00 10–34 Hg2Br2 5.60 10–23
CaCO3 (calcite) 4.50 10–9 Hg2I2 4.70 10–29
4. Argentometric titrations
One of the oldest analytical techniques that started in the mid–1800’s
Silver nitrate (AgNO3) is commonly used as titrant and the end point are
observed as follows:
a. Formation of a secondary colored precipitate – Mohr method
Developed by Karl Friedrich Mohr (1806-1879) in 1865
Titrant: AgNO3
Titration reaction: Ag+(aq) + Cl–1(aq) AgCl(s)
white
Chemical and Physical Principles Analytical Chemistry
Indicator: K2CrO4
Indicator reaction: 2Ag+(aq) + CrO4–2(aq) Ag2CrO4(s)
yellow red
In practice, the indicator concentration is kept between 0.002 M to 0.005 M
Titration is done at a pH of 8 to avoid precipitation of silver as hydroxide
(above pH of 10) and eliminate formation of HCrO 4–1 (below pH of 6) which
results to consumption of more titrant
Usually a low concentration of chromate is desired to detect the end point
clearly since a chromate ion imparts an intense yellow color
b. Formation of a colored complex – Volhard method
Developed by Jacob Volhard (1834-1910) in 1874
Titrant: KSCN
Back titration: Ag+(aq) + Cl–1(aq) AgCl(s)
excess white
Ag+(aq) + SCN–1(aq) AgSCN(s)
white
Indicator: ferric alum, NH4Fe(SO4)212H2O
Indicator reaction: Fe+3(aq) + SCN–1(aq) Fe(SCN)+2(aq)
red
Titration is done in acidic medium using HNO3 with indicator concentration
of about 0.01 M
For the titration of chloride, the resulting precipitate is filtered off before the
back titration since it reacts with the titrant and is more soluble than AgSCN
For the titration of iodide, the indicator is not added until all iodide is
precipitated since the dissolved iodide is oxidized by the ferric ion
c. Formation of a colored adsorption complex – Fajans Method
Developed by Kazimierz Fajans (1887-1975) in 1926
Titrant: AgNO3
Titration reaction: Ag+(aq) + Cl–1(aq) AgCl(s):Cl–1. . . . DCF–1
excess white greenish-yellow
Indicator: fluorescein, dichlorofluorescein or eosin
Indicator reaction: Ag+(aq) + Cl–1(aq) AgCl(s):Ag+1:DCF–1
excess white pink
Before the equivalence point, chloride anion adsorbs to the precipitate in the
primary adsorption layer and drives the adsorption dye anion away by
electrostatic repulsion and the dye imparts a greenish-yellow color in
solution
As soon as the equivalence point is just exceeded with the presence of excess
silver ion, this ion now adsorbs to the precipitate in the primary adsorption
layer where the oppositely-charged adsorption dye anion adsorbs to the
counter-ion layer and imparts a pink color in solution
For titration of chlorides, fluorescein may be used at an optimum pH range
between 7-10 while dichlorofluorescein is used in acidic solution of pH
greater than 4.4
For bromides, iodides and thiocyanates, eosin is used for titration in acidic
medium of pH between 1-2 imparting magenta color at the end point
Dextrin is added to prevent excessive coagulation of the AgCl precipitate
Chemical and Physical Principles Analytical Chemistry
G. Complexation Titration
1. Important terminologies
Ligand – molecule or ion which possesses at least one unshared pair of electron
capable of forming coordinate covalent bond with an ion
Coordination complex or metal complex – formed when a metal ion is bonded to
monodentate ligands
Chelate complex – formed when a metal ion is bonded to a polydentate ligand
Chelants – chemicals that form soluble complex molecules with a metal ion
which results to inactivation of the ion’s ability to react with other elements to
produce precipitates
2. Titration methods involving complexes
a. Determination of cyanide – Liebig method
The titration is carried by the dropwise addition of AgNO 3 in a solution of a
cyanide forming a soluble cyanide complex of silver:
2CN–1 + Ag+ Ag(CN)2–1
The endpoint of the titration is the formation of a permanent faint turbidity:
Ag(CN)2–1 + Ag+ Ag [Ag(CN)2](s)
b. Determination of nickel
An ammoniacal solution of nickel is treated with a measured excess of
standard cyanide solution:
Ni(NH3)6+3 + 4CN–1 + 6H2O Ni(CN)4–1 + 6NH4OH
The excess cyanide is determined according to the Liebig method
c. Titration with ethylenediaminetetraacetic acid (EDTA)
The structure suggests six potential sites (hexadentate) for metal bonding –
the four carboxyl groups and two amino groups
Reagents for EDTA titration
Free acid, H4Y – can be used as a primary standard when dried for
several hours from 130C to 145C and dissolved completely with small
amount of base
Disodium EDTA dihydrate, Na2H2Y2H2O – analytical reagent grade is
commercially available and usually dried at 80C for 24 hours
NH3-NH4Cl buffer solution (pH = 10) – prepared from 17.5 grams of
NH4Cl and 142 mL of concentrated NH3 and
Indicators for EDTA titration
Eriochrome Black T or Solochrome – used for titrations with pH more
than 6.5 since it polymerizes in strongly acidic solutions; color changes
between pH range of 7-11 from royal blue to wine red;
Calmagite – similar to EBT but color change is sharper and its aqueous
solution is stable; used for titration at pH = 10 using NH3-NH4Cl buffer
Solutions of EDTA combines with any metal ions in a 1:1 ratio
O
C
O OH O O
H2C H2
C CH2 O C C C
N O
HO N CH2 CH2 H2C
+ M+n M
H2C H2C N OH H2C
N O
C OH H2C C C C
H2
H2C
O
O
O O C
O
Chemical and Physical Principles Analytical Chemistry
Step 2: Identify oxidation and reduction reactions and indicate the number of
electrons lost or gained, respectively
Oxidation: NO2–1 NO3–1 + 2e–
+3 +5
Reduction: MnO4–1 + 3e– MnO2
+7 +4
The equilibrium constant and the standard electrode potential are related as
follows:
nε
log K (T = 298.15 K, = 0 and Q = K)
0.05916 V
VmL, sample
Na 2S2 O3 VNa
mL, blank
S O M Na 2S2 O3
1 I2
2 Na 2S2O3
253.80mg I 2
1 mmol I 2
101 cg
mg
Iodine Number 2 2 3
VmL, sample
Na 2S2 O3 VNa
mL, blank
S O M Na 2S2 O 3
1 meq Na 2S2O3
1 mmol Na 2S2 O3
Peroxide Value 2 2 3
V mL
Na 2S2O3 M Na 2S2 O3 1 mmol O 2
4 mmol Na 2S2 O3
1 mmol O2
32 mg O
Dissolved oxygen 2
VmL, blank
Fe2
V mL,2sample M
Fe2
1 mmol K 2 Cr2O 7
6 mmol Fe2
4 mmol K
6 mmol O 2
2 Cr2 O 7
1 mmol O2
32 mg O
COD Fe 2
εbVSCS εbVX C X
As kVSCS kVX C X mCS b
VT VT
where k = b/VT, m = kVS and b = kCXVX
Chemical and Physical Principles Analytical Chemistry
2. Analysis of mixtures
The total absorbance of a solution at a given wavelength is equal to the sum of the
absorbances of the components in the mixture
At 1: A1 ε x1 bC x ε y1 bC y
At 2: A 2 ε x 2 bC x ε y 2 bC y
3. Photometric titration
Plot of absorbance versus volume of titrant where the curves consist of two
straight line regions with different slopes
The end point is the intersection of the extrapolated linear regions
analyte = 0
product > 0
Absorbance
A titrant = 0 B C
Volume of Titrant
2. Analytical methods classified as micro analysis uses sample mass ranging from
a. < 1 mg b. 1-10 mg c. 10-100 mg d. > 100 mg
3. Chemical which are tested by the manufacturers showing the actual percentages of
impurities and labeled on the containers are called __________.
a. reagent grade chemicals c. certified reagent
b. analytical reagent d. all of these
4. Platinum crucibles can be used for the following processes without significant loss
except
a. Fusion with sodium carbonate, borax or alkali bifluorides
b. Evaporation with hydrofluoric acid
c. Ignition of oxides of Ca and Sr
d. Heating with sulfides
Chemical and Physical Principles Analytical Chemistry
7. What volume of water must be added to concentrated HCl solution to prepare 100
mL 0.955 M HCl solution?
a. 7.9 mL b. 15.8 mL c. 46.0 mL d. 92.1 mL
8. What grade of water as defined by the British Standard 3978 is suitable for the
determination of trace quantities which can be prepared by the distillation of de-
ionized water?
a. Grade 1 b. Grade 2 c. Grade 3 d. Grade 4
9. % wt/vol
a. 17 b. 19 c.21 d. 23
12. The following describes colloidal suspensions formed during precipitation except
a. These particles are almost invisible to the naked eye
b. They settle readily from a given solution
c. They are not easily filtered
d. none of the these
13. A 1.5176 g sample of a CaCO3 was dissolved in an acidic solution. The calcium was
precipitated as CaC2O4H2O (146.11) and the ignited precipitate at 230C was found
to weigh 0.8249 g. What is the percentage of CaO (56.08) in the sample?
a. 20.9% b. 23.8% c. 41.8% d. 47.6%
For numbers 14 to 16…
To a solution containing a precipitate of PbS, an excess of H 2S was added.
17. A mixture containing FeCl3 (162.20) and AlCl3 (133.33) only weighs 750.8 mg. The
chlorides were precipitated using ammonia and ignited to Fe2O3 (159.69) and Al2O3
(101.96), respectively. The oxide mixture weighs 351.3 mg. Calculate the percentage
of Al (26.98) in the sample.
a. 15.5% b. 41.2% c. 43.3% d. 58.8%
18. Which of the following does not describe the correct way to wash precipitates?
a. Minimum volume of washing liquid must be used to wash the precipitate
b. Wash with small portions of washing liquid
c. For very soluble precipitates, ionic salts containing common ion must be
added to the washing liquid
d. Gelatinous precipitates requires more washing than crystalline precipitates
19. What weight of Mn ore should be taken so that the percentage of MnO 2 (86.94) in
the ore would be twice the mass of Mn3O4 (228.82) precipitate obtained in milligram?
a. 19.0 mg b. 38.0 mg c. 57.0 mg d. 76.0 mg
20. Process by which an agglomerated colloid return to it dispersed state during washing
due to leaching of electrolyte responsible for its coagulation
a. nucleation b. coagulation c. agglomeration d. peptization
21. A 5.488-gram sample containing MgCl2 (95.21) and NaCl (58.45) was dissolved in
sufficient to give 1L solution. Analysis of chloride content of a 250 mL aliquot
resulted in the formation of 2.462 gram AgCl. The magnesium in a second 100 mL
aliquot resulted in the formation of 0.2610 gram of Mg 2P2O7 (222.53) after treatment
with (NH4)2HPO4. Determine the percentage of NaCl in the sample.
a. 12.7% b. 23.2% c. 36.1% d. 40.7%
23. What is the extent of ionization of the second proton of 0.5 M H 2SO4 at 25C?
a. 1% b. 2% c. 4% d. 8%
24. Which of the following aqueous solutions of the same concentration will have the
largest pH value at 25C?
a. NH3 b. KCl c. NH4Cl d. NaF
25. Which of the following solutions at 25C will have the lowest pH value?
a. 0.15 M Na2SO4 (KA2 of H2SO4 = 1.2 10–2)
b. 5.2 10–8 M HCl
c. 0.05 M NaCN (KA of HCN = 6.2 10–10)
d. 0.01 M NH4Cl (KA of NH4+ = 5.6 10–10)
26. Which of the following acid-base pairs will result in the formation of a buffer
solution when titration is done before the equivalence point?
a. NaOH and HCl c. NH3 – HBr
b. KOH – HNO3 d. all of these
Chemical and Physical Principles Analytical Chemistry
29. What concentration of acetic acid is needed to prepare a buffer solution with pH =
4.50 and a buffer capacity of 0.10 M-pH–1?
a. 0.067 M b. 0.122 M c. 0.174 M d. 0.225 M
30. Approximately how many grams of NH4Cl (53.45) should be dissolved in a liter of
0.125 F NH3 to reduce the concentration of hydroxide ions to one-thousandth of its
original value?
a. 79.1 g b. 62.5 g c. 11.7 g d. 7.91 g
32. 0 mL
a. 1.26 b. 2.84 c. 4.07 d. 5.12
33. 15 mL
a. 1.57 b. 1.71 c. 1.86 d. 2.04
34. 25 mL
a. 1.44 b. 2.88 c. 5.76 d. 6.64
35. 49.9 mL
a. 4.39 b. 7.39 c. 8.37 d. 12.18
39. In the standardization of an acid solution with primary standard sodium carbonate,
why is it necessary to boil the solution before completing the titration?
a. to eliminate the reaction product, carbon dioxide and carbonic acid
b. to destroy the buffering action of the resulting solution due to the presence of
carbonic acid and unreacted hydrogen carbonate
c. to achieve a sharper endpoint with methyl red indicator due to the large
decrease in pH
d. all of the these
40. Calculate the molarity of NaOH solution if 12.25 mL was used to titrate 0.2615 gram
of primary standard KHP.
a. 0.1045 b. 0.1354 c. 0.2509 d. 0.1697
41. What is the best basis for choosing the right indicator for a given acid – base titration
from among the following?
a. type of acid c. pH at equivalence point
b. type of base d. molarity of the acid or base
42. In standardizing a solution of NaOH against 1.431 grams of KHP, the analyst uses
35.50 mL of the alkali and has to run back with 8.25 mL of acid (1mL = 10.75 mg
NaOH). What is the molarity of the NaOH solution?
a. 0.2118 M b. 0.2044 M c. 0.7831 M d. 0.2598 M
43. In the titration of a weak acid with a strong base, which of the following is the best
indicator to be used?
a. bromocresol green c. methyl red
b. methyl orange d. phenolphthalein
44. A 0.2055-g sample of calcite (impure CaCO3) is treated with 27.18 ml of 0.0712 N
HCl and the excess is found to require 5.44 ml of 0.0869 N NaOH for back titration.
Calculate the percentage purity of calcite in terms of % wt/wt CaCO3 (100).
a. 17.8% b. 35.6% c. 53.4% d. 71.2%
45. Process of determining the nitrogen content of organic materials by mixing the
sample with powdered copper (II) oxide and ignited to a combustion tube giving CO 2,
H2O, N2 and small amounts of nitrogen oxides.
a. Kjeldahl Method c. Winkler Method
b. Dumas Method d. Wij’s Method
46. A 640 mg sample of P2O5 (141.94) contains some H3PO4 (97.995) impurity. The
sample is reacted with water and the resulting solution is titrated with 0.867 M
NaOH requiring 20.7 mL to the thymolphthalein end point. Calculate the percentage
of impurity in the sample.
a. 0.90% b. 1.80% c. 2.70% d. 3.60%
47. In the titration of phosphoric acid, which of the following statements is true?
a. Titration curve contains three inflection points since it is a triprotic acid
b. Phenolphthalein indicator is used to detect the second end point.
c. It can be treated as a monoprotic or diprotic acid during titration
d. all of these
Chemical and Physical Principles Analytical Chemistry
50. What is the % wt NaOH for the sample containing a mixture of NaOH-Na2CO3?
a. 1.82% b. 5.22% c. 10.64% d. 11.13%
51. In the analysis of nitrogen using Kjeldahl Method, which of the following is added to
decompose organic matrices present in the sample?
a. H2SO4 b. HgO c. K2SO4 d. H2O2
52. A 7.279-gram sample of meat was analyzed for its nitrogen content using Kjeldahl
Method. Upon digestion, the ammonia liberated was collected in 250 mL of 0.855 M
H3BO3. The resulting solution was titrated with 37.25 mL of 0.3122 M HCl using
mixed indicator. Determine the % protein in the sample using 6.25 as factor for meat
products.
a. 13.98% b. 2.24% c. 19.69% d. 3.14%
53. Which of the following is NOT used as primary standard for the standardization of
alkali solutions?
a. HgO b. H2C2O4 c. HSO3NH2 d. C6H5COOH
55. Assuming butter comprised mainly of fat, what is its molar mass?
a. 475 b. 970 c. 1445 d. 1940
57. In the determination of chloride using Mohr method, what should be the theoretical
molar concentration of the chromate ion indicator given that K SP of Ag2CrO4 is 1.1
10–12?
a. 0.002 b. 0.004 c. 0.006 d. 0.008
59. A 1.500-gram sample of impure aluminum chloride was dissolved in water and
treated with 45.32 mL of 0.1000 M AgNO3 using K2CrO4 as indicator. Express the
analysis in %AlCl3 (133.33).
a. 40.28% b. 13.43% c. 4.48% d. 27.36%
61. A mixture of LiBr (86.845) and BaBr 2 (297.22) weighing 800 mg is treated 50.00
mL of 0.1879 M AgNO3 and the excess is found to require 8.76 mL of 0.3179 M
KSCN for back titration, using ferric alum as indicator. What is the percentage of
BaBr2 in the sample?
a. 67.95% b. 32.05% c. 35.62% d. 64.38%
62. In Volhard Method, why is it necessary to carry out titration in acidic solution?
a. To prevent precipitation of iron as hydrated as hydrated oxide
b. To prevent formation of AgSCN precipitate
c. To prevent reduction of halide
d. To prevent precipitation of silver as hydrated as hydrated oxide
63. A 750.25-gram alloy of nickel was dissolved and treated to remove the impurities. Its
ammoniacal solution was treated with 50 mL of 0.1075 M KCN and the excess
cyanide required 2.25 mL of 0.00925 M AgNO 3. Determine % Ni (58.69) in the
alloy.
a. 20.86% b. 37.69% c. 10.53% d. 41.72%
64. Which of the following is true about Liebig method for determination of cyanide?
a. The titration process requires an indicator to signal the end of titration
b. The addition of excess amount of AgNO3 produces an insoluble compound
c. A red complex of silver with cyanide is formed which signals the end of the
titration process
d. The ratio of silver to cyanide is 2:1 with a permanent faint turbidity as the
endpoint
66. Which of the following ions is best titrated with EDTA at minimum pH less than 7?
a. Ca+2 b. Sr+2 c. Mg+2 d. Fe+3
68. An EDTA solution was prepared by dissolving the disodium salt in 1L of water. It
was standardized using 0.5063 gram of primary standard CaCO 3 and consumed
28.50 mL of the solution. The standard solution was used to determine the hardness
of a 2L sample of mineral water, which required 35.57 mL of the EDTA solution.
Express the analysis in terms of ppm CaCO3.
a. 89 ppm b. 316 ppm c. 158 ppm d. 269 ppm
70. The 300 mg sample of impure Na2SO4 (142.04) was dissolved in sufficient water and
the sulfate was precipitated by the addition of 35.00 mL of 0.1022 M BaCl2. The
precipitate was removed by filtration and the remaining BaCl 2 consumed 6.79 mL of
0.2467 M EDTA for titration to the Calmagite endpoint. Calculate the purity of the
sample.
a. 80% b. 85% c. 90% d. 95%
71. A 0.8521 gram sample of an alloy was found to contain Cu (63.55) and Zn (65.41)
with small amounts of Pb (207.2) and Hg (200.59). The sample was dissolved in
nitric acid and diluted to 500 mL. A 10 mL aliquot was treated with KI to mask the
Hg and the resulting solution required 7.06 mL of 0.0348 M EDTA solution. A
second 25 mL aliquot was treated with ascorbic acid and the pH was adjusted to 2.00
to reduce Hg+2 and the metallic Hg was removed from the solution. To this solution,
thiourea was then added to mask the Cu and the resulting solution required 8.58 mL
for titration. The lead ion was titrated in a 250 mL in the presence of NaCN to mask
Cu, Zn and Hg and required 3.11 mL for titration. Calculate the percentage of Cu
and Hg in the sample of alloy.
a. 47% Cu and 3% Hg c. 53% Cu and 7% Hg
b. 44% Cu and 5% Hg d. 56% Cu and 5% Hg
72. Commonly, the analyte in a sample is present in two different oxidation states. Pre-
reduction is then necessary before titration. One of the metallic reductors is zinc
soaked in a dilute solution of mercuric chloride. This reductor is known as
__________.
a. Walden reductor c. Lindlars catalyst
b. Devarda Alloy d. Jones reductor
73. At pH = 7 and a pressure of 1 bar, the potential for the half reaction, 2H+(aq) + 2e–
H2 (g) is __________.
a. 0 V b. –0.414 V c. –0.828 V d. –1.255 V
Chemical and Physical Principles Analytical Chemistry
74. Which of the following is false about iodine as an oxidizing agent in titration?
a. Standard iodine solutions have low smaller electrode potential
b. Sensitive and reversible indicators are readily available
c. Iodine is very soluble in water and losses are minimal
d. The solution lacks stability and requires regular standardization
75. What is the molarity of a KMnO4 solution standardized against 1.356 gram Na2C2O4
(134 g/mol) requiring 25.1 mL of the solution in acidic medium?
a. 0.161 M b. 0.403 M c. 1.008 M d. 0.856 M
76. Which of the following statements is true on the determination of chemical oxygen
demand?
a. For solutions with high chloride content, addition of sulfamic acid is necessary
to eliminate the chloride interference
b. Chemical oxygen demand accounts for the oxygen demand of both
biodegradable and non-biodegradable oxidizable pollutants in a body of water
c. The interference caused by the nitrite ion is eliminated by the addition of
HgSO4 which oxidizes this ion to its nitrate form
d. all of these
77. A sample of iron ore weighing 385.6 mg was dissolved in acid and passed through a
Jones reductor. The resulting solution 52.36 mL of 0.01436 M K 2Cr2O7 for titration
to the diphenylamine sulfonic acid endpoint. Calculate % Fe 3O4 (231.55 g/mol) in the
ore sample.
a. 15.05% b. 45.15% c. 90.30% d. 67.98%
79. A sample of pyrolusite weighing 0.2400 gram was treated with excess KI. The iodine
liberated required 46.24 mL of 0.1105 M Na 2S2O3 solution. Calculate % MnO2
(86.94) in the sample.
a. 46.27% b. 30.85% c. 92.54% d. 76.12%
81. A 10.00 gram sample of cooked-ham was pureed with 200 mL of water, filtered and
the resulting solution containing dissolved potassium nitrite was acidified. This
solution was treated with 25.00 mL of 0.00514 M KMnO4 was back titrated with
14.97 mL of 0.01678 M FeSO4. Calculate the amount of nitrite (46.01) in ppm.
a. 450 b. 900 c. 1350 d. 1800
83. A 100 mL water sample was analyzed by Winkler Method. If 7.52 mL of 0.0124 M
Na2S2O3 was used for titration, determine ppm O2 in the water sample.
a. 2.8 b. 3.5 c. 6.4 d. 7.5
Chemical and Physical Principles Analytical Chemistry
84. The following volumes of standard solutions containing 20 ppm Fe+2 were added to
10-mL aliquot samples of waste water in 500-mL volumetric flasks. Excess
thiocyanates ion was added and the resulting solutions were diluted up to the mark
and the following absorbance were obtained in a 1.00-cm cell:
Volume of standards, ppm 0 5 10 15 20 25
Absorbance 0.095 0.281 0.433 0.628 0.806 0.972
Calculate the concentration of Fe+2 in the waste water.
a. 5.5 ppm b. 8.3 ppm c. 11.0 ppm d. 16.5 ppm
85. A 500 mg sample of a solution containing cobalt (58.93) and nickel (58.69) was
dissolved and diluted to 50 mL. A 25 mL aliquot was treated with a complexing
agent to produce a colored complex and the volume was adjusted to 50 mL. The
following data were obtained for the simultaneous determination in a 1.00-cm cell:
Wavelength Molar absorptivity, [M–1-cm–1] Absorbance of
(nm) Co Ni solution, A
510 36400 5520 0.815
656 1240 17500 0.314
Calculate the concentration of Co in the solution in ppm
a. 1172 ppm b. 1940 ppm c. 2142 ppm d. 2343 ppm