Analytical Chemistry

Dr. Leonardo C. Medina, Jr.

1. A neutral molecule such as ethanol or sugar which has found its way into the pores of a typical anion-
exchange resin can be eliminated
a. only by replacement with a action
b. only replacement with an anion
c. only if replaced by another organic molecule on a one-for-one exchange basis
d. by flushing out with water
2. In chromatography, a substance for which the distribution coefficient, K, is zero may be used to estimate
a. the volume within the column available to the moving phase
b. the volume within the column occupied by the packing
c. the volume within the pores of the packing material
d. the total volume of the column
3. Which of the following statements is false in normal phase adsorption?
a. The more polar compound, the more strongly it will be adsorbed from a solution
b. A high molecular weight favors adsorption, others factors being equal
c. The more polar the solvent, the stronger the adsorption of the solute
d. The adsorption isotherm is usually nonlinear
4. The best measure of the quantity of a solute in LC is
a. the height of the elution band
b. the area of the elution band
c. the baseline width of the elution band
d. the retention volume
5. Which of the following would be the fastest way to decide which adsorbent and what solvent system to use
for large-scale chromatographic separation of an organic reaction product from materials formed in side
reactions?
a. Paper chromatography
b. Affinity chromatography
c. TLC
d. Adsorption chromatography with gradient elution
6. To deionize tap water by ion exchange for laboratory use, the best approach employs
a. a column containing a strong-acid cation exchanger in the hydrogen form
b. a column containing a strong-base anion exchanger in the hydroxyl form
c. a mixed-bed column containing a strong-acid cation exchanger in the sodium and a strong-base
anion exchanger in the chloride form
d. a mixed-bed column containing a strong acid cation exchanger in the hydrogen form and a strong-
base anion exchanger in the hydroxyl form
7. In chromatography, a substance for which the distribution coefficient, K, is zero may be used to estimate
a. the volume within the column occupied by the packing material
b. the total volume of the column
c. the volume within the pores of the packing material
d. the volume within the column available to the mobile phase
8. The purpose of the solid support material in a GLC column is to
a. Immobilize the stationary liquid phase
b. Adsorb sample components that are insufficient soluble in the stationary liquid phase
c. Provide a “backup” stationary phase in the event that a liquid is lost by evaporation
d. Remove impurities from the carrier gas
9. Helium, rather than nitrogen, is sometimes used as the carrier gas in GLC because
a. being lighter than nitrogen, helium elutes the sample components more rapidly
b. helium is less expensive than nitrogen
c. nitrogen has stable isotopes which separate and cause anomalous column behavior
d. of its much higher thermal conductivity

1
10. An important feature of open-tubular GLC columns is:
a. they can accept much larger sample than can packed columns because of their great length
b. solute partitioning between stationary and mobile phases is very rapid and the C term in the van
Deemter equation is relative small
c. they permit the use of a wider variety of carrier gases
d. they can be operated at temperatures closer to the boiling point of the stationary liquid phase than
can packed columns and thus handle less volatile samples
11. Raising the column temperature in GLC decreases solute retention times primarily because
a. solute diffusion coefficients in the liquid phase decrease with increasing temperature
b. van der Waals interactions between solutes and stationary phase are stronger at higher
temperatures
c. gases are generally less soluble in liquids at higher temperatures
d. detector sensitivity is a function of temperature, especially with a thermal conductivity cell
12. Which of the following would have practically no effect upon the retention volume of a solute GLC?
a. changing the carrier-gas flow rate
b. increasing the stationary liquid loading of the column packing from 5 to 10% by weight
c. increasing the column temperature
d. changing the chemical nature of the stationary liquid
13. the separation factor, S, in chromatography depends upon
a. the length of the column
b. the square root of the length of the column
c. the nature of the stationary liquid phase
d. the number of theoretical plates in the column
14. In the GLC, interaction of solutes with the solid support will often cause
a. unusually narrow elution bands
b. asymmetric elution bands with “tailing”
c. excessive eddy diffusion
d. decreased detector sensitivity
15. Increasing the quantity of stationary liquid phase applied to the column packing will, with everything else the
same,
a. increase tR for a solute
b. decrease tR for a solute
c. not influence tR for a solute
d. decrease the nonequilibrium term in the van Deemter equation
16. Line spectra are emitted by:
a. Incandescent solids
b. Excited molecules
c. Molecules in the ground electronic state
d. Excited atoms and monatomic ions
17. Band spectra are emitted by:
a. Tungsten lamps and Nernst glowers
b. Excited molecules in the vapor phase
c. Excited atoms and monatomic ions
d. Incandescent solids
18. A chemist is conducting research on the development of analytical methods based upon chemiluminescence.
If a conventional spectroflourometer is used for the measurements, and the instrument has separate
switches for its various circuits, which switch will be left in the “off” position?
a. Detector power supply
b. Amplifier
c. Source power supply
d. Power to the motor drive of the scanning monochromotor on the emission side of the instrument
19. The hydrogen or deuterium discharge tube can be used as a source of continuous ultraviolet radiation for
spectrophotometers because of:
a. The characteristics of chopper-modulated radiation
b. Pressure broadening of hydrogen or deuterium emission lines
c. The great sensitivity of photomultiplier tubes

2
 d. The narrow band pass of modern grating monochromators
20. Chopping the source beam in conjunction with the used of the tuned ac amplifier in an atomic absorption
spectrophotometer accomplishes the ffg:
a. A recording potentiometer can be used instead of a voltmeter for the readout
b. A less sensitive detector can be used instead of the usual photomultiplier tube
c. A cooler frame can be used without decreasing the population od ground-state atoms
d. Radiation emitted by excited atoms in the frame will not interfere with the absorbance
measurement
21. Line spectra are emitted by:
a. Hot solids
b. Excited polyatomic molecules
c. Molecules in the ground electronic state
d. Excited atoms and monatomic ions
22. Recording spectrophotometers sometimes operate with feedback loops that vary the power of the beam
through the sample. This mode of operation:
a. Eliminates the need for continuous source
b. Requires two monochromators
c. Eliminates the need for nonabsorbing solvents
d. Makes the detector a null device, with the result that nonlinear response to radiant power would not
be deleterious
23. Which of the following best explains why atomic absorption is sometimes more sensitive than flame emission
spectroscopy?
a. At the temperature of a typical flame, the pollution of ground-state atoms is much greater than the
pollution of excited atoms
b. Detectors employed in absorption work are inherently more sensitive than those used to measure
emission
c. Hollow cathode discharge tube have a much greater radiant power output that do ordinary flames
d. An absorption line in a flame is always much sharper than an emission line because of the Doppler
effect
24. The method of standard addition compensates for matrix effects provided:
a. The addition does not dilute the sample appreciably and does not itself introduce appreciable
quantities of interfering substances
b. The addition dilutes the sample enough that the concentration of interfering substances are
lowered to negligible values
c. The addition contains none of the substance being determined
d. The addition contains a large enough quantity of some substance to swamp out sample
25. Fe3+ and Cu2+ form complexes with EDTA. The ferric complexes is colorless, as is Fe 3+ itself, at the
concentration involve here; the copper complex is a deep blue color (deeper than the color of Cu2+ itself),
while EDTA is colorless. The photometric titration curve below was obtained when a solution containing both
Fe3+ and Cu2+ was titrated with EDTA using a spectrophotometer set at a wavelength of 745 nm in the visible
region of the spectrum.
26.

A
B

ml of EDTA solution

3
 a. A is the iron end point
b. B is the iron end point
c. The distance from A to B on the milliliter axis represents the quantity of iron
d. The quantity if the iron could not be calculated from a graph like this unless the quantity of copper in the
solution was known ahead of time
27. If a current-time curve is recorded during a controlled-potential electrolysis, the number of coulombs is found
from
a. the slope of the curve where t = 0 (the initial slope)
b. the time required to reach zero current
c. the slope of a tangent to the curve when the electrolysis is halfway to completion
d. the area under the curve
28. Which factor represents the most severe limitation on the sensitivity of a conventional polarographic
analysis?
a. The capacitance or charging current which flows as each mercury drop develops
b. The sensitivity of galvanometers and other current-measuring devices
c. The uncertainty in the potential of the DME resulting from the iR drop through the test solution
d. Liquid junction potentials of uncertain magnitude
29. Concentration overpotential is associated with
a. a slow electron-transfer process
b. concentration gradients in the solution near the electrode interface
c. unusually low activity coefficients
d. the large iR drops through the solution
30. Activation overpotential is associated with
a. inefficient stirring, leading to concentration gradients in the solution near the electrode surface
b. slow mass transfer across liquid junctions
c. a slow step in the overall electrode process, including chemical steps following electron transfer
d. slow movement of electrons is aqueous solutions
31. If an analyst ran a voltammogram on a dilute solution of cadmium chloride containing no other solutes, using
a platinum microelectrode and stirring the solution, cadmium ion would be transported to the electrode by
a. convection
b. diffusion
c. electrical migration
d. all the above processes
32. The residual current in palography
a. is always anodic
b. is always cathodic
c. may be anodic or cathodic depending upon the potential of the DME
d. is eliminated by the supporting electrolyte
33. The major purpose for employing the “method of standard addition” in analytical chemistry is to
a. increase sensitivity through an increase in the measured value
b. decrease sensitivity when the analyte solution is too concentrated
c. compensate for matrix effects
d. compensate for operator errors
34. In a controlled-potential electrolysis, the number of moles of electrons added to the reducible species at the
cathode is given by
a. ne = CF
b. ne = C/F
c. ne = F/C
d. ne = moles of electrons, C = number of coulombs, F = the Faraday, i = current, R = resistance
35. Which of these reactions does not require a catalyst to obtain a convenient rate?
a. Titration of oxalate with cerium(IV)
b. Titration of arsenic(III) with KMnO4
c. Titration of arsenic(III) with cerium(IV)
d. Titration of arsenic(III) with iodine at pH 8.5
36. Which of these statements is true?
a. In the McBride procedure the titration is carried out rapidly at room temperature

4
 b. Acidic solutions of permanganate are not stable
c. The oxidation of Cl‾ by MnO4¯ is slow in the presence of Fe2+
d. Fe2+ is a weaker reducing agent than Cl¯
37. Which of these statements is true?
a. In an iodometric process iodine acts as reducing agent
b. K2Cr2O7 is a stronger oxidizing agent than KMnO4 in 1 M acid
c. The Ce4+ ion hydrolyzes readily in solutions of low pH
d. I2 is adsorbed on the surface of α-amylose to give a blue color
38. When 1 mol of glycerol is oxidized by periodic acid, the organic products are
a. 2 mol of formaldehyde
b. 2 mol of formic acid
c. 1 mol of formaldehyde +2 mol of formic acid
d. 2 mol of formaldehyde + 1 mol of formic acid
39. The reaction between arsenic(III) and I2 is forced to the right by
a. raising the pH
b. lowering the pH
c. adding starch
d. adding KI
40. The emf of a cell made up of an electrode of unknown potential and SCE os 0.65 V with the calomel
electrode negative. The potential (V) of the unknown electrode referred to H2 is
a. -0.90
b. +0.40
c. +0.90
d. -0.40
41. Given the redox couple
TiO2+ + 2H+ + e ↔ Ti3+ + H 2O
Eo = +0.10 V
If the pH is decrease by 1 unit, the potential of the couple will
a. become more positive by 2 X 0.059 V
b. become more negative by 2 X 0.059 V
c. become more positive by 0.059/2 V
d. become more negative by 0.059 V
42. In the titration of Fe2+ with Ce4+, the equilibrium potentials developed by the Fe3+ -Fe2+ and the Ce4+ -Ce3+
couples will be equal
a. only at the EPt
b. only halfway to the EPt
c. throughout the titration
d. never
43. Which of these expressions is correct?
a. 2.3RT/F = 0.059 at 298oC
b. nEO = + 0.059 Log K
c. EO = -∆GO/nF
d. All of the above
44. Given
A3+ + e ↔ A2+ Eo = + 1.42 V
B + 2e ↔ B
4+ 2+ Eo = + 0.40 V
In the titration of B with A , the potential at the EPt (V) is
2+ 3+

a. 0.61
b. 0.71
c. 0.91
d. 1.08

45. The salt whose relative solubility is most increased by increasing the ionic strength of the solution is
a. AgI
b. CuCl
c. CaSO4

5
 d. AlPO4
46. An example of back-titration is
a. the Volhard determination of Ag+
b. the Volhard determination of Cl¯
c. the Mohr determination of Cl¯
d. the determination of Cl¯ using an adsorption indicator
47. The salt with the smallest molar solubility is
a. AgBr
b. Zn(OH)2
c. Ag2C2O4
d. Ag3AsO4
48. Which of the following salts lead should show the greatest percentage increase in solubility for a tenfold
increase in [H+]?
a. PbF2
b. PbCl2
c. PbBr2
d. PbI2
49. In which solution is Ag2CrO4 least soluble?
a. 0.001 M K2CrO4
b. 0.01 M K2CrO4
c. 0.001 M AgNO3
50. Which compound is more soluble at pH 2 than at pH 3?
a. BaF2
b. CdCO3
c. Fe(OH)2
d. All of the above
e. None of the above
51. 50 mL of 0.10 M NaCl is titrated with 0.10 M AgNO3. In a second titration 50 mL of 0.10 M NaBr is titrated
with 0.10 M AgNO3. Which of the following statements is false?
a. At the start of the titrations pCl = pBr
b. When 25 mL of titrant is added in each titration, pCl = pBr
c. At the EPts, pLC > pBr
d. When 60 mL of titrant is added in each titration, pCL < pBr
52. The Ksp for Ag2S is 4 X 10-48, the Ksp for NiS is 1 X 10-25. If 1 mmol of Ni2+ is added to 100 mL of a solution
containing solid Ag2S in equilibrium with Ag+ and S2- ions, what will happen?
a. NiS will precipitate
b. More Ag2S will dissolve
c. More Ag2S will precipitate
d. Both a and b
e. Both a and c
53. At the equivalence point in the titration of CrO24- with Ag+,
2Ag+ + CrO24- ↔ Ag2Cr04(s)
a. pAg + 2pCrO4 = pKsp
b. 3pAg + 2 log 2 = pKsp
c. 3pCrO4 = pKsp + 2 log 2
d. All of the above
54. Which statement concerning α4, the fraction of EDTA in the Y4¯ form, is correct?
a. α4 increases as the pH increases
b. –log α4 increases as the [H+] increases
c. +log α4 increases as the pH decreases
d. All of the above
e. Only two of the above
55. At pH 7 the predominant form of EDTA is
a. H3Y¯
b. H2Y2¯
c. HY3¯

6
 d. Equal amounts of H2Y2¯ and HY3¯
56. Consider the titration of Zn2+ with EDTA. Which statement below is true?
a. The action is more complete the lower the pH
b. The titration is more feasible at high [H+] that low [H+]
c. The titration is more feasible in 0.010 M NH3 than in 0.10 M NH3
d. All of the above are true
e. None of the above are true
57. 40 mL of 0.025 M Cu2+ is titrated with 0.040 M EDTA at pH 9. When 50 mL of titrant is added
a. log [Cu2+] = -log Keff
b. log [Cu2+] = pKeff
c. pCu = -pKeff
d. all of the above
e. none of the above
58. Which of these statements is true?
a. The effective stability constant depends upon the pH
b. A Lewis acid is an electron donor
c. A ligand is a Lewis base
d. Two of the above are true
e. All of the above are true
59. To 50 mL of 0.10 M H3PO4 is added 50 mL of 0.15 M NaOH. In the resulting solution
a. [H2PO4¯] ≈ [H3O+]
b. [H3PO4] ≈ [H2PO4-]
c. [H2PO4-] ≈ [HPO24-]
d. [H3PO4] ≈ [HPO24-]
60. To 50 mL of 0.12 M H3PO4 is added 50 mL of 0.30 M NaOH. The pH of the resulting solution is
approximately
a. 12.32
b. 9.77
c. 7.21
d. 11.50
61. To 50 mL of 0.08 M Na3PO4 is added 40 mL of 0.020 M HCl. The pH of the resulting solution is
approximately
a. 9.77
b. 7.21
c. 4.67
d. 2.12
62. What is the value of the equilibrium constant of the reaction
CO2-3 + 2H2O ≈ H2CO3 + 2OH-
Where Kb1 and Kb2 are the hydrolysis constants of CO2-3 and HCO3¯, respectively?
a. Kb1 X Kb2
b. K/Kb1 X Kb2
c. Kb1/Kb2
d. Kb2/Kw
63. What is the value of the equilibrium constant of the reaction
H3PO4 + 2OH¯ ↔ HPO2-4 + 2H2O
a. Ka1Ka2/Kw
b. Ka1Ka2/Kw2
c. Ka1Kw/Ka2
d. Kw/Ka2
64. NaOH is added to a solution of leucine (H2L+, pKa1 = 2.33; HL, pKa2 = 9.72) until the pH reaches a value of
6.04. At this pH the species in highest concentration is
a. HL
b. L¯
c. H2L+
d. [HL] ≈ [L¯]

7
 65. For the acid H2A, pKa1 = 7.00 and pKa2 = 11.00, which of the following indicators is most suitable for the
titration (0.10 M solution)
A2¯ = 2H3O+ → H2A + 2H2O
a. phenolphthalein
b. bromthymol blue
c. methyl red
d. methyl orange

Questions 65-71 are based on the following information:

Given the following acids, bases and indicators
________________________________________________________________________
Acid pKa Base pKb Indicator
HA Strong MOH Strong I (base), pKb = 9
HB 4.40 NOH 8.80 II (acid), pKa = 5
HC 9.10 ROH 4.10 III (base), pKb = 5

66. Which titration/s is/are feasible (0.10 M solution)?

a. HC with NaOH
b. ROH with HCl
c. HA with NaOH
d. NOH with HCl
e. Two of the above
67. Which titration/s is/are feasible (0.10 solution)?
a. NCl with NaOH
b. NaC with NaOH
c. HA with NaOH
d. All of the above
e. None of the above
68. HB is titrated with 0.10 M NaOH. Which is the proper indicator?
a. I
b. II
c. III
d. I and II
69. Which is the strongest conjugate base?
a. OAc¯
b. F¯
c. NO2¯
d. OCl¯
70. Which of these salts can be titrated feasibility?
a. NaNO2 with HCl
b. CH3NH3Cl with NaOH
c. NaCN with HCl
d. NH4Cl with NaOH
e. Two of the above
71. Which titration (0.10 M solution) will give the largest change in pH at the EPt?
a. Benzonic acid with NaOH
b. Formic acid with NaOH
c. Pyridine with HCl
d. Monochloroacetic acid with NaOH
72. Which of these statements is true?
a. An aprotic solvent has acidic properties
b. The titration reaction is more complete the smaller the autoprotolsis constant
c. Dissociation into ions is necessary for successful acid-base titrations
d. A low dielectric constant is desirable for amphiprotic solvents

8
73. An aqueous solution is made by mixing equal volumes of 0.10 M NaOH. Which equation is corredt6 for this
solution?
a. [H3O+] + [OH-] = [Na+] + [OAc-]
b. [HOAc] + [OAc-] = 0.10
c. [H3O+]+ [Na+] = [OH-] = [OAc-]
d. More than one above
74. For a 0.10 M solution of Na2SO4, which equation is correct?
a. [H3O+]+ [Na+] =[OH-]+[HSO4-] + 2[SO42-]
b. [HSO4-] + [SO42-] = 0.10
c. [Na+] = 0.20
d. All of the above
75. Which of these compounds should increase in solubility in acid solution?
a. KCL
b. CaF2
c. Ba(OH)2
d. NaClO4
e. Two of the above
76. Which of the following is the most basic solution?
a. pH= 10
b. pH= 5
c. [OH-]= 10-12
d. [H3O+] = 10-12
77. Which statement is true?
a. Addition of NaOAc to a solution of HOAc increase the pH.
b. Addition of NH3 to a saturated solution of AgCl causes more AgCl to dissolve
c. Addition of NH4Cl to a solution of NH3 lowers pH.
d. All of the above.
e. None of the above is true
78. In a solution in which [H3O+] = 10,
a. pH= 1
b. pH= -1
c. pOH= 15
d. More than one above
79. A precipitate of Fe(OH)3 is contaminated with Mg(OH)2. The best way to get rid of the impurity is
a. Washing
b. Digestion
c. Ignition
d. Reprecipitaion
80. Colloids which carry down only a small quantity of water when coagulated are said to be
a. Lyophobic
b. Suspensiods
c. Emulsiods
d. Two of the above
81. The process of dispersing an insoluble material into a liquid as a colloid called
a. Occlusion
b. Nucleation
c. Peptization
d. Coagulation
82. Which of the following does not promote the formation of large crystals of CaC2O4? H2C2O4 is a weak acid.
a. Slow mixing of dilute solutions
b. Decreasing (Q – S)/ S
c. Digestion
d. Precipitation at high pH rather than low pH
83. AgCl is precipitated by adding AgNO3 to an aqueous NaCl solution. The ion most strongly adsorbed to the
surface of the colloidal particles before the EPt is
a. Na+

9
 b. Cl¯
c. Ag+
d. H3O+
84. One part per million is the sane as
a. 1 mg/kg
b. 1 μg/g
c. 1 ng/mg
d. All of the above
85. The normality of a 0.10 M solution of KMnO4 is
a. 0.50
b. 0.30
c. 0.10
d. More information is needed to answer this
86. Suppose the substance A, molecular weight MW, reacts with permanganate as follows:
5A + 2MnO4¯ + . . . → 2Mn2+ + . . .
The EW of A in this reaction is MW divided by
a. 2
b. 3
c. 4
d. 5
87. One of the chief ores of uranium is pitchblende, U3O8. When pitchblende is treated with HNO3, uranyl nitrate,
UO2(NO3)2, is formed. The EW of U3O8 in this reaction is MW divided by
a. 2
b. 3
c. 2/3
d. 3/2
88. A sample is analyzed and reported to contain 21% NaOH. Later it is found that the basic material is KOH
rather than NaOH. The percentage NaOH in the sample is
a. 29.4
b. 37.5
c. 21
d. 15
89. How many coulombs of electricity are required to liberate 11.2 mL (STP) 0f O2 gas by reaction
2H2O → 4H+ + O2 + 4e
a. 96.5
b. 96.5/2
c. 96.2 X 2
d. 96.5 X 4
90. The average of 64 results is how many more times reliable than the average of 4 results?
a. 2
b. 4
c. 8
d. 16
91. Which of these statements is true?
a. The variance is the square root of the standard deviation
b. Precise values are always accurate
c. The number 0.02040 contains only four significant figures
d. Two of the above are true
92. Students performed an analysis obtaining a percentage purity of 18.54% and a relative standard deviation
4.0 ppt. Later they discovered they had made an error of a factor of 2 and that the result should have been
9.27%. What is the correct relative standard deviation in ppt?
a. 2.0
b. 4.0
c. 8.0
d. √2.0

10
93. Titrator A obtains a mean value of 12.96% and a standard deviation of 0.05 for the purity of a sample. Titrator
B obtains corresponding values of 13.12% and 0.08. The true percent purity is 13.08. Compared the titrator
B, titrator A is
a. Less accurate but more precise
b. More accurate and more precise
c. Less accurate and less precise
d. More accurate but less precise

11