Tran Le Huy – K61 Advanced Chemistry CHEM 222

HOMEWORK 01
A. Concentrations, solution preparation and stoichiometric calculation.

Problem 1.32. A bottle of concentrated aqueous sulfuric acid, labeled 98.0 wt% H2SO4, has a
concentration of 18.0 M.

(a) How many milliliters of reagent should be diluted to 1.000 L to give 1.00 M H2SO4?

(b) Calculate the density of 98.0 wt% H2SO4.

Solution:

(a) Applying dilution formula: Mconc × Vconc = Mdil × Vdil

Mdil 1.00 M
 Vconc = Vdil M = 1000 mL ( 18.0 M ) = 55.6 mL
conc

mol 1L
(Molarity)× (molar mass of solute) 18 × × 98.079 g/mol
L 1000 mL
(b) Density = = = 1.80 g/mL
(percent concentration) 98%

Problem 1.33. What is the density of 53.4 wt% aqueous NaOH (FM 40.00) if 16.7 mL of the solution
diluted to 2.00 L gives 0.169 M NaOH?

Solution:

Applying dilution formula: Mconc × Vconc = Mdil × Vdil

Vdil 2000 mL
 Mconc = Mdil = 0.1690 M ( ) = 20.24 M
Vconc 16.7 mL

mol 1L
(Molarity) ∗(molar mass of solute) 20.24 × × 40 g/mol
L 1000 mL
Density = = = 1.516 g/mL
(percent concentration) 53.4%

Problem 1.34. How many milliliters of 3.00 M H2SO4 are required to react with 4.35 g of solid
containing 23.2 wt% Ba(NO3)2 if the reaction is Ba2+ + SO42- → BaSO4(s)?

Solution:

mBa(NO3 )2 = 23.2% (4.35 g) = 1.01 g

1.01 g
 nH2 SO4 = nBa(NO3 )2 = 261.34 g/mol = 3.86 × 10-3 mol

3.86 × 10−3
 VH2 SO4 solution = mol =1.29 mL
3.00 × 0.001 L/mL
L

Problem 1.35. How many grams of 0.491 wt% aqueous HF are required to provide a 50% excess to
react with 25.0 mL of 0.023 6 M Th4+ by the reaction Th4+ + 4F- → ThF4(s)?
Solution:

nTh4+ = (0.0250 L)(0.0236 M) = 5.90 × 10-4 mol

nHF(necessary) = nF− = 4nTh4+ = 2.36 × 10-3 mol

nHF(in excess) = 1.5(2.36 × 10-3 mol) = 3.54 × 10-3 mol

mHF = (3.54 × 10-3 mol) × 20 g/mol = 70.8 × 10-3 g

70.8 × 10−3
maqueous HF = 0.491%
= 14.4 g

Problem 1.45. Sulfamic acid is a primary standard that can be used to standardize NaOH.
+
H3NSO3- + OH- → H2NSO3- + H2O

Sulfamic acid

FM 97.094

What is the molarity of a sodium hydroxide solution if 34.26 mL react with 0.333 7 g of sulfamic
acid?

Solution:
0.3337 g
nsulfamic acid = = 3.4369 × 10-3 mol = 3.4369 mmol
97.094 g/mol

3.4369 mmol
nNaOH = nOH− = nsulfamic acid  Molarity of NaOH solution = 34.26 mL
= 1.003 M

Problem 1.46. Limestone consists mainly of the mineral calcite, CaCO3. The carbonate content of
0.541 3 g of powdered limestone was measured by suspending the powder in water, adding 10.00 mL
of 1.396 M HCl, and heating to dissolve the solid and expel CO2:

CaCO3(s) + 2H+ → Ca2+ + CO2↑ + H2O

Calcium carbonate

FM 100.087

The excess acid required 39.96 mL of 0.100 4 M NaOH for complete titration. Find the weight
percent of calcite in the limestone.

Solution:

nHCl(total) = (10.00 mL)(1.396 M) = 13.96 mmol

nHCl(titrated with NaOH) = (39.96 mL)(0.1004 M) = 4.012 mmol

 nHCl(consumed by carbonate) = 13.96 – 4.012 = 9.948 mmol

 1
nCaCO3 = 2 nHCl(consumed by carbonate) = 4.974 mmol  mCaCO3 = 0.4978 g

0.4978 g
wt% CaCO3 = 0.5413 g × 100% = 91.96%

B. Answer these following questions

1. List primary standards that can be used in acid-base titration and redox titration? Can KMnO4
and NaOH be primary standard?
Some examples of primary standards used in acid-based titrations include potassium
hydrogen iodate (KH(I03)2), sodium borate, sodium carbonate (Na2CO3). Examples of primary
standards used in redox titrations include pure iron, NaC2O4 (sodium oxalate), As2O3 (arsenic
trioxide), K2Cr2O7 (potassium dichromate), KBrO3 (potassium bromate), KIO3 (potassium iodate)
and KH(IO3)2 (potassium hydrogen iodate).
NaOH and KMnO4 are not primary standards. Solid NaOH is highly hygroscopic (it
absorbs water from the air) and thus it cannot be accurately weighed. It also absorbs carbon
dioxide from the air, forming sodium carbonate and thereby reducing the amount of sodium
hydroxide present. This means that a NaOH solution of known molarity cannot be directly
prepared without resorting to an air-and-water-free environment. We can only prepare a solution
of NaOH that has the approximate concentration we will need. KMnO4 cannot be used as
primary standard because it cannot be obtained in very pure form, readily reacts with the traces of
organic material or other reducing substances in water and it is also photosensitive.

2. Which factors can influence to your titration error? Explain.

 End Point Error
Changes in color can indicate the endpoint of a titration. The end point of a titration is when
the reaction between the two solutions has stopped. Indicators, which change color to indicate
when the reaction has stopped, do not change instantly. In the case of acid-base titration, the
indicator may first lighten in color before changing completely. Also, each individual perceives
color slightly differently, which affects the outcome of the experiment. If the color has changed
slightly, too much of the titrant, which comes from the burette, can be introduced into the
solution, overshooting results.
 Misreading the Volume
The accuracy of titration requires precise measurement of the volume of materials in use. But
markings on a burette can be easily misread. One way to misread the volume is by looking at the
measurement on an angle. From above, it can seem like the volume is lower, while from below,
the apparent volume looks higher. Another source of measurement error is looking at the wrong
spot. A solution forms a concave curve and the bottom of the curve is used to measure the
volume. If the reading is taken from the higher sections of the curve, the volume measurement
will be in error.
 Concentrations
Residue from cleaning can affect the accuracy of titration. Errors in concentrations directly
affect the measurement accuracy. Errors include using the wrong concentration to begin with,
which can occur from chemical decomposition or evaporation of fluids. The solution may have
been prepared incorrectly or contaminatns could have been introduced into the solution, such as
 using dirty equipment. Even the process of cleaning your equipment, if carried out with the
wrong solution, can affect the concentrations of the solutions to be experimented on.
 Using the Equipment Incorrectly
You must follow strict guidelines in handling and using all equipment during the experiment
as the slightest mistake can create errors in the findings. For example, swirling the solution can
result in loss of solution that will affect results. Errors in filling the burette can cause air bubbles
that affect the flow of the liquid in the burette.
 Other Errors
Other human or equipment errors can also creep in. Human error includes using selecting the
wrong reagents or using the wrong amount of indicator. Equipment error typically is in the
burette, which can develop leaks over time. Even a small loss of fluid will affect the results of the
titration.

3. To determine traces of analytes in sample, is it possible to use reagents that are prepared in tap
water?
Dilutions cannot be prepared using tap water. Problems arise if the water used for a dilution is not
of the highest quality – especially if it contains additional analyte or interferences

4. For accurate measurement, is it possible to prepare standards in a beaker instead of a volumetric

flask?
No, it is NOT possible. Beakers are used primarily for crudely measuring out large volumes of
liquids, mixing reagents and carrying out chemical reactions. The graduated markings on a beaker
are only approximate, so a beaker should never be used for accurate volume measurements.
Volumetric flasks typically measure a single volume via a single mark on a tall narrow neck.
These flasks are generally used for solution preparation.