Assay of Aromatic Spirit of Ammonia

for Ammonium Carbonate

I.Principles Involved
- Residual titration with blank determination

- Type of reaction: Neutralization

- Titration conditions:

- Away from light

- Cool temperature

- Two indicators used:

- Phenolphthalein - endpt: colorless solution (8.0-10.0)

- Methyl Orange - endpt: faint pink color (3.2-4.4)

 Uses of Aromatic Ammonia Spirit for Ammonium
Carbonate
- Respiratory stimulant

- Used for treating syncope (fainting)

- Has antacid and carminative properties

- Liquefying expectorant

- Also called smelling salt

(Ammonia Spirit, Aromatic, 2004)

Official Requirement
Aromatic Ammonia Spirit is a hydroalcoholic
solution that contains, in each 100 ml, not less
than 1.7 g and not more than 2.1g total NH3, and
Ammonium Carbonate corresponding to not less
than 3.5 g and not more than 4.5 g (NH4)2CO3.
II. Reason for Important Steps
1.Transfer 10.0 ml to a flask about 300-ml capacity
Away from light - Aromatic ammonia spirit, USP is light sensitive

(USP 35 NF 30, 2012, p. 2188)

II. Reason for Important Steps
2. Add 30 ml of 0.5 N NaOH, and boil until the mixture, replacing the water lost
by evaporation until the vapor no longer turn moistened red litmus paper blue.

Addition of NaOH with boiling liberates NH3.

- Detected by red litmus to blue (Svehla, 1996, p. 160)

(NH4)2CO3 + 2NaOH 2NH3 + H2O + Na2CO3

(Soine & Wilson, 1961, p. 311)

(Svehla, 1996, p. 160)

II. Reason for Important Steps
Ammonia

- removed from the solution

- unstable in aqueous solution

- Affects pH of solution

- Ammonium carbonate decomposes into ammonia and ammonium bicarbonate.

(NH4)2CO3 NH4HCO3 + NH3

NH3 + H2O NH4OH

(Soine & Wilson p, 1961, p. 317)

II. Reason for Important Steps
Water - added to compensate loss due to evaporation

Boiling:

- Eliminates CO2

- Eliminates carbonate/bicarbonate buffer region

(Laitinen & Harris, 1975, p. 111)

II. Reason for Important Steps
3. Cool, dilute with 100 mL of cold, carbon dioxide-free water.

CO2 is soluble in water and produces a very weak acid known as carbonic acid,
H2O + CO2 -
H2CO3

H2CO3 + H20 H30+ + HCO3- (K1 = 5.0 X 10-7)

HCO3- + H20 H30+ + C032- (K2 = 4.6 X 10-11)

CO2 lowers the pH of the solution and interferes with the end point due to C032 -/
HCO3- buffer region.
(Christian, 2004, pp. 279, 280)

(Soine & Wilson, 1961, p. 501)

II. Reason for Important Steps
4. Add about 6 drops of phenolphthalein TS. Add just enough 0.5 N sulfuric acid
VS to discharge the color of phenolphthalein

Phenolphthalein (pH 8.0 -10.0)

- used to detect the first endpoint.

- used to get an approximation of where the second endpoint will occur.

- is colorless beyond the first endpoint and does not interfere.

II. Reason for Important Steps
Addition of H2SO4 enables complete neutralization of NaOH. Consequently,
the phenolphthalein endpoint detects the transformation of carbonate to
bicarbonate

2NaOH + H2SO4 Na2SO4 + H2O

NaOH + H2CO3 Na2CO3

2Na2CO3 + H2SO4 Na2SO4 + 2NaHCO3

(Skoog, et.al., 2014, p. 383)
II. Reason for Important Steps
5. Add methyl orange and titrate with 0.5 N sulfuric acid VS

Methyl orange (pH 3.2-4.4) yellow to faint pink

- Used for bicarbonate to carbon dioxide

- used as indicator for the second titration to visualize the neutralization of the
NaHCO3, a weaker base produced in the neutralization of Na2CO3 which is
outside the pH transition range of phenolphthalein.

2NaHCO3 + H2SO4 Na2SO4 + 2CO2+ 2H2O

(Knevel & Digangi 1977, p. 67)

(Christian, 2004, p. 280)

II. Reason for Important Steps

Further titration with H2SO4 is performed to completely

neutralize NaHCO3 which liberates carbon dioxide gas from
the buffer system HCO3-/CO2, leaving only HCO3- in the
solution.

(Soine & Wilson, 1961, p. 207)

(Christian, 2004, p. 280)

II. Reason for Important Steps
6. Perform a blank determination

A blank determination is performed to account for the presence of sodium

carbonate in the sodium hydroxide solution which might have interfered with the
endpoint.

Sodium hydroxide reacts with CO2 forming Na2CO3 and adsorbed water
Carbonate ion in the solution decreases the sharpness of endpoints.

( Harris, 2010, p. 223)

(Skoog, et., al. 2014, p. 386)
III. Chemical Reactions
1. (NH4)2CO3+ 2NaOH 2NH3+ Na2CO3 + 2H2O

2. 2Na2CO3 + H2SO4 2NaHCO3 + Na2SO4

3. 2NaHCO3 + H2SO4 Na2SO4 + 2H2O + 2CO2

2Na2CO3 + 2H2SO4 2Na2SO4 + 2H2O + 2CO2

Factor: 2, 2 H+ ions were transferred in the overall equation

IV. Sample Computation
Sample weight (g) = NT VT (/)

1000

= 0.5N 30 mL 96.09 (/)

2 1000

= 0.7207g Na2CO3
IV. Sample Computation
Since Official Requirement:

3.5 23 = 0.7207 23

100

4.5 23 = 0.7207 23

100

= 16.02 20.59mL
References:

Ammonia spirit, aromatic (Inhalation-systemic). (2004, July 31). Retrieved from www.drugs.com/mmx/ammonia-spirit-aromatic.html.
Christian, G. (2004. Analytical Chemistry (6th ed.). USA: John Wiley and Sons Inc., pp. 279-280
Harris, D.C. (2010). Quantitative Chamical Analysis (8th ed.). USA: W.H. Freeman and Company, p. 223.
Knevel, A., & DiGangi, F. (1977). Jenkins Quantitative Pharmaceutical Chemistry (7th ed.). New York : McGraw-Hill, p. 67.
Laitinen, H. , & Harris W. (1975). Chemical Analysis an Advanced Text and Reference (2nd ed.). New York : McGraw- Hill, p. 111.
Mosby (2017). Mosbys medical dictionary (10th ed.). Missouri: Elsevier, p.134
Skoog, D. A., West, D. M., Holler, J. F., Crouch, S. R.(2014). Fundamentals of Analytical Chemistry. USA : Brooks/Cole, Cengage Learning, p. 386,
383.
Soine, T.O., & Wilson, C. O. (1961). Rogers Inorganic Pharmaceutical Chemistry (7th ed.). Philadelphia: Lea & Febiger, pp. 207, 311, 317, 501.
Svehla, G. (1996). Vogel's Qualitative Inorganic Chemistry (7th edition). Essex, England: Longman Group Limited. p. 160, 212
United States Pharmacopeial Convention, Inc. (2012). United States Pharmacopeia 35th Revision and National Formulary 30th Edition. Maryland,
USA: USPCI. p. 2188.