CHE 1316

Laboratory Measurements & Techniques

LECTURE 7
Calculations of Gravimetric Analysis
Precipitation Titrations
Electrochemistry

www.baylor.edu/chemistry
 Gravimetric Calculations
1. Need to know:
1. Composition of substance weighed
2. Weight of substance weighed
3. Relationship between moles of substance sought
and moles of substance weighed through balanced
chemical equation(s)

2. Then substitute into:

molsought = molweighed × S.R.

Wt.sought Wt.weighed
=
M.M.sought M.M.weighed
 Gravimetric Calculations
The Fe in a 1.1324 g sample of iron ore is precipitated as Fe 2O3  x H2O
by the addition of aqueous NH3. The residue is ignited at high
temperature to give 0.5394 g of pure Fe2O3 (M.M. = 159.69 g/mol).
Calculate the wt% Fe (M.M. = 55.847 g/mol) in the ore.

2 Fe3+ + 6 OH− → Fe2O3  x H2O + (3-x)H2O

Fe2O3  x H2O + heat → Fe2O3 + x H2O

1 Fe2O3  x H2O 2 Fe
mol Fe = mol Fe2O3 × ×
1 Fe2O3 1 Fe2O3  x H2O

Wt. Fe 0.5394 g Fe2O3 2 Fe

= ×
55.847 g/mol 159.69 g/mol 1 Fe2O3

0.3773 g
Wt. Fe = 0.3773 g  wt% Fe = × 100% = 33.32%
1.1324 g
 Gravimetric Calculations
Based on information given in the previous example, determine the
Wt% Fe3O4 (M.M. = 231.53 g/mol).

mol Fe3O4 = mol Fe2O3 × S.R. (???)

choose a and b so that element of

“sought” × a interest is equal in the numerator
S.R. =
“weighed” × b and denominator (typically NOT
H or O).

a × Fe3O4 2 Fe3O4 Fe = 6 in both numerator and

S.R. = =
b × Fe2O3 3 Fe2O3 denominator

Wt. Fe3O4 0.5394 g Fe2O3 2 Fe3O4

= ×
231.53 g/mol 159.69 g/mol 3 Fe2O3
 Precipitation Titrations
Analytical Reaction is a Precipitation

• Precipitate is not collected and weighed

• Calculations are identical to acid-base titrations
• Precipitation must be fast
• Indicators are difficult to find

Argentometric Titrations involve precipitation of AgX with AgNO3

Mohr Method: Direct titration of X− with primary standard AgNO3

Volhard Method: Excess AgNO3 used to precipitate AgX. Excess

Ag+ is back-titrated with standardized KSCN.

(Typical analytes include: Cl−, Br−, I−, CN−, SCN−, …)

 Mohr Titrations
Direct titration of X− with a standard solution of AgNO3

ANALYTICAL REACTION: AgNO3 + X− → AgX(s) + NO3−

white

INDICATOR: CrO42− ion from K2CrO4

2 AgNO3 + CrO42− → Ag2CrO4(s) + 2 NO3−

yellow red

AgX(s) precipitates before Ag2CrO4(s)!!!

Titration Error is Important:

Titration of a sample containing only K2CrO4 (“blank”) affords correction

Veq pt = Vend pt − Vblank.

 Mohr Titrations
A 0.4179 g sample containing chloride and inert material is titrated with
0.1012 M AgNO3, requiring 34.99 mL to reach the Ag2CrO4 end point.
Titration of a blank sample consumes 0.32 mL of the AgNO 3 titrant.
Determine the Wt% chloride (M.M. = 35.453 g/mol) in the sample.

Veq pt = Vend pt − Vblank = 34.99 mL − 0.32 mL = 34.67 mL

AgNO3 + Cl− → AgCl(s) + NO3−

mol AgNO3 = mol Cl−

Wt. Cl−
0.1012 M × 34.67 mL =
35.453 mg/mmol

124.4 mg
Wt. Cl = 124.4 mg  Wt% Cl =
− −
× 100% = 29.77%
417.9 mg
 Volhard Method
Another Example of a Back-Titration!!!

ANALYTICAL REACTIONS:

1. Add excess Ag+ as standard AgNO3: Ag+ + X− → AgX(s)

white

2. Back-titrate with standard KSCN: Ag+ + SCN− → AgSCN(s)

white

INDICATOR: Fe3+

Fe3+ + SCN− → Fe(SCN)2+

red

AT THE EQUIVALENCE POINT:

mmol Ag+ = mmol X− × S.R.X + mmol SCN− × S.R.SCN

 Redox Reactions
Oxidizing Agent (Oxidant): Accepts e−’s
Reducing Agent (Reductant): Donates e−’s

Red1 + Ox2 Ox1 + Red2

Half Reactions:
Oxidation (anode) Red1 Ox1 + n e E1
Reduction (cathode) Ox2 + n e Red2 E2

E = E1 + E2

Redox Titrations can only be performed if E > 0

 Suggested Problems

• Problem Set 6 (lab manual):

1-5, 13-17, 19-22, 25, 26