Group 1, WAD, Chem 27.

DETERMINATION OF PHOSPHORUS
BY GRAVIMETRIC ANALYSIS

Introduction
a set of methods of quantitative analysis in which the
mass of the analyte is determined using the mass of a
compound to which it is chemically related

Introduction

most inorganic anions and cations

neutral species
(e.g., water, sulfur dioxide, carbon dioxide, and iodine)
organic substances
(e.g., lactose, salicylates, nicotine, cholesterol)

Introduction

Introduction

Introduction
Properties of an ideal precipitating agent:
Specific: reacts with only one chemical species
Selective: reacts with a limited number of chemical
species
Produces a precipitate that is:

Sparingly soluble
Stable and unreactive
Easily filtered and washed
Of known chemical composition once dried or ignited

Introduction
Colloidal Suspension
Smaller particles

Crystalline Suspension
Larger particles

Do not settle spontaneously Tend to settle

(Brownian movement)
spontaneously
Not easily filtered

Easily filtered

Crystalline suspensions have greater particle size,

making them easier to filter and wash, while avoiding
loss of sample that could lead to errors.

Introduction
Objectives of the experiment:
1. To isolate phosphorus in the unknown
sample as magnesium pyrophosphate
(MgP2O7)
2. To calculate the percent of phosphorus in
the unknown sample from the weight of
magnesium pyrophosphate

Methodology

Weigh Whatman no. 40 filter paper in analytical balance.

Record weight.

Store in desiccator until needed.

Use gloves when handling filter paper!

Methodology

Calculate and weigh amount of magnesium chloride hexahydrate

(MgCl26H2O) needed to prepare 100 mL of 5% (w/v) solution.

Place solid into beaker with 60 CO2-free distilled water. Stir until the solid was
completely dissolved.

Transfer solution to a 100-mL volumetric flask.

Methodology

Calculate and measure amount of concentrated NH3 needed to

prepare 250 mL of 2 M solution.

Transfer into a beaker with 150 mL of CO2-free distilled water and

mix thoroughly.

Transfer to 250-mL volumetric flask and dilute to mark, then

transfer to a plastic bottle.

Methodology

Weigh 0.30 0.31 grams of unknown sample by difference using

the analytical balance.

Transfer into 500-mL beaker with 50 mL of CO2-free distilled water

and stir until dissolved.

Add 60 mL of the 5% (w/v) MgCl26H2O solution to beaker. Then,

slowly add 200 mL of 2 M NH3 mixture, while stirring.

Discussion
Precipitating agents:
Magnesium chloride hexahydrate
Ammonia
optimal conditions require basic solution (pH 9)
magnesium ammonium phosphate is slightly soluble in
alkaline solutions
NH4(aq) + H2O(l) NH3(aq) + OH-(aq)
OH-(aq) + H2PO4-(aq) H2O(l) + HPO42-(aq).
MgCl26H2O(s) + HPO42-(aq) + NH3(aq) [Mg(NH4)PO46H2O](s)
OR
5H2O(l) + HPO42-(aq + NH4(aq) + Mg2+(aq) + OH-(aq) [Mg(NH4)PO46H2O](s)

Discussion
QS
RS =
S
Accounts for the effect of certain variables on
particle size of precipitate formed
Relates the particle size to a single property of
the system, the relative supersaturation (RS)

Q = solute concentration at any time

S = equilibrium solubility

Discussion
colloidal
precipitate

QS
RS =
S

crystalline
precipitate

Discussion
Mechanisms of precipitate formation
Nucleation: few ions, atoms, or molecules joining into a stable
solid that usually forms on the surface of suspended contaminants
Particle growth: ions, atoms, or molecules deposit on existing
particles instead of forming new nuclei

The dominating mechanism determines the particle size of freshly

formed precipitate.
The rate of nucleation varies directly with relative supersaturation.

Discussion
NUCLEATION

QS
RS =
S

(large number of
small colloidal
precipitate)
PARTICLE GROWTH

(smaller number
of crystalline
precipitate)

Discussion
Minimized relative
supersaturation

Particle
growth

Crystalline
suspension

Larger
particle
size

Easier to
filter

Higher temperatures increase solubility (S) of the precipitate

Dilute solutions of reactants decrease Q
Slowly adding reagents to the solution prevents high
concentration of solute at one point in time (Q)
Vigorous stirring induces colloid to coagulate into larger
particles
Controlling pH (e.g., magnesium ammonium phosphate is
sparingly soluble in alkaline solutions)
(Precipitates such as hydrous oxides and sulfides cannot form crystals due to their low
solubility.)

Methodology

Cover beaker with watch glass and allow to stand for 20 minutes.

Filter out precipitate using Whatman no. 40 filter paper and an

appropriately sized funnel.

Wash completely-filtered precipitate twice using 10-mL portions of

CO2-free distilled water and 95% ethanol.

Discussion
Why was the solution left to stand undisturbed?
Digestion: process in which a freshly formed precipitate is
left in the precipitating solution
Produces larger, cleaner particles and a denser mass
Results from the dissolution and recrystallization occuring
constantly in solution while digesting
Recrystallization bridges adjacent particles together,
producing larger crystals that are more easily filterable

Discussion
Whatman No. 40 filter paper
Used specifically for
quantitative analyses
Medium porosity
Ashless (does not affect mass
of sample during ignition)

Discussion
Why was the solution washed?
CO2-free distilled water removes impurities and breaks up
counter-ion layer of colloid
Peptization (aggregated colloid returns to its dispersed
state) may occur
To counteract peptization: 95% ethanol recovers dispersed
particles yet easily evaporates upon drying/igniting

Methodology

Remove filter paper from funnel and spread onto a Petri dish.

Air-dry filter paper in fume hood overnight, then dry in an oven at

110C until completely dry.

Cool filter paper in desiccator for 15 minutes and weigh final

product.

Discussion
Why was the precipitate dried in an oven after air-drying?
Removes leftover solvent and volatile species from
precipitate (e.g., ethanol wash)
Hydrate was removed and magnesium ammonium
phosphate was produced

2[Mg(NH4)PO46H2O](s) MgNH4PO4(s) + 6H2O(l)

Discussion
but, wait!
After drying, precipitate should have been ignited
to yield magnesium pyrophosphate
Some precipitates are ignited in order to
decompose them into a suitable weighing form
Weighing form: compound with a known composition
that is used to find analytes weight

This step, however, was not carried out in the

experiment.
2[Mg(NH4)PO46H2O](s) Mg2P2O7(s) + 2NH4(g) + 11H2O(g) + 2OH

Results
Trial

Weight of filter paper

1.548 g

Weight of filter paper and sample

3.460 g

Weight of Mg(NH4)PO4

1.912 g

Weight of P in sample

0.4313 g

Weight of sample

0.3077 g

% P in sample

140.2%

Actual weight of P in sample

30.97 g

Actual % P in sample

21.82%

% relative error

542.4%

Calculations

mass P = mass MgNH 4 PO4

1 mol MgNH 4 PO4

1 mol P
FW P

FW MgNH 4 PO4 1 mol MgNH 4 PO4 1 mol P

1 mol MgNH 4 PO4

1 mol P
30.97376 P
mass P = 1.912 g

137.31746 MgNH 4 PO4 1 mol MgNH 4 PO4

1 mol P
mass P = 0.4312767591g = 0.4313g

mass analyte
100
mass sample
0.4312767591g
%P=
100
0.3077 g
% P = 140.1614427% P = 140.2% P
%P=

Calculations

AW P
% actual P =
100
MW Na2 HPO4
30.97376 g
% actual P =
100
141.961514 g
% actual P = 21.818142% actual P = 21.82% actual P

Calculations

Xi Xt
% Er =
100
Xi
21.81842% 140.1614427%
% Er =
100
21.81842%
% E r = 542.3929872% E r = 542.4% E r

Discussion
542.4% ERROR?!
Magnesium ammonium phosphate was not ignited
Further removes impurities from the precipitate
Produces magnesium pyrophosphate (more suitable
weighing form than magnesium ammonium phosphate)

Magnesium ammonium phosphate as weighing form

Less stable with indefinite composition (not certain if all
of the hydrate has been removed when the precipitate
was dried)

Guide Questions & Answers

1. Give factors that affect the particle size of a precipitate and
explain how each factor affects particle size.
A. Temperature: higher temperatures increase solubility, affecting S.
B. Reactant concentrations: dilute solutions of reactants have lower
concentrations, decreasing Q.
C. Rate at which reactants are mixed: slowly adding reagents to the
solution prevents having a high concentration of solute at one
point in time, thus lowering Q.
D. Stirring: vigorous stirring reduces the volume of the outer layer of
the colloid, inducing the colloid to coagulate into larger particles;
also prevents localized high concentration sites.
E. Digestion: having the precipitation process occur for a longer
period of time allows molecules on the surface of smaller
particles to dissolve and then reform on the surface of larger
particles.

Guide Questions & Answers

2. What are the properties of an ideal precipitating
agent?
Specificity and selectivity are two properties of an ideal
precipitating agent. Specific precipitating agents react with
only one chemical species, while selective precipitating
agents react with a limited number of chemical species.
Additionally, an ideal precipitating agent should react with
the analyte to produce a precipitate that is sparingly soluble,
easily filtered and washed, and of known chemical
composition once dried or ignited.

Guide Questions & Answers

3. Define the following terms: peptization, digestion,
weighing form.
Peptization: the process in which an aggregated colloid
returns to its dispersed state.
Digestion: the process in which a freshly formed precipitate
is left (usually with heating) in the precipitating solution,
resulting in larger, cleaner particles and a denser mass.
Weighing form: the compound of known composition that
results from the filtering and drying of the gravimetric
precipitate; called as such because it is the form in which
the sample is weighed in order to quantify the analyte.

Conclusion & Recommendations

Gravimetric analysis is based on the measurement of the
analytes mass.
The analyte in this particular experiment was phosphorus in
the form of MgNH4PO4 (theoretically, Mg2P2O7), while the
precipitating agents were MgCl2H2O and NH3.
The analyte must first be separated by forming a precipitate,
which is then filtered, washed, and dried/ignited until a
compound with a definite composition is obtained.
The weight of the analyte can be determined from the weight of
the sample through stoichiometry.

Conclusion & Recommendations

Certain variables, such as temperature, concentration, etc., can
be manipulated in order to yield more effective results.
Although gravimetric analyses produce accurate results,
multiple errors can be introduced during the experiment due to
factors like lack of time or materials.
The major error in the experiment was the failure to ignite the
sample and obtain a suitable weighing form (Mg2P2O7),
resulting in a very high percent error.
It is recommended that the procedure should be followed at all
times, and done carefully while performing gravimetric analysis.