UNIVERSITY OF GUYANA

FACULTY OF NATURAL SCIENCES

DEPARTMENT OF CHEMISTRY

CHM 3202 – Analytical Chemistry (I)

LECTURER: Dr. Dawn Fox

Lab # 2
The Determination of Sulphate by Gravimetric
Analysis

Name: Dayshawn Billingy Group Member: William Ross

Reg #:13/0705/1877
Date: 11th April,2014
ABSTRACT

The aim of this experiment is to perform a gravimetric analysis with the intent of finding the

percentage of sulphate present in the sample. The sample was pre-dried in the oven after which

0.629g of the sample was weighed in a piece of paper. After weighing, the sample was dissolved

using 230mL of distilled water and 0.5 mL concentrated HCL. The solution was then heated to

near boiling and 0.25M BaCl2 was added until precipitation was complete. The beaker was then

left to digest on a steam bath until the supernatant liquid was clear. During this time, a crucible

was weighed and heated then left to cool in a desiccator. The contents of the beaker were then

filtered. Following this, the precipitate was washed with hot distilled water and dilute HNO3.

AgNO3 was added as a test for residual chloride. The filter paper was placed into the crucible

carefully. The crucible was then heated gently in order to drive off the moisture then the charring

process began. After the charring process was complete, the precipitate and crucible were placed

in the desiccator to cool. H2SO4 was then added to the precipitate and it was heated gently to

burn off the acid. The contents were again cooled and then weighed until a constant weight had

been met.

The raw data was then collected and the necessary calculations were done. This includes

mean, standard deviation, confidence interval and % of sulphate. The results and calculations

were tabulated.

In conclusion, the percentage of Sulphate found in the precipitate was found to be 36.2%.
INTRODUCTION

In this experiment you will determine the percentage (by mass) of sulphate in an unknown

sulphate salt by gravimetric analysis. First you will dissolve a measured mass of the unknown

salt in water. Next you will add an excess of aqueous barium chloride to the aqueous solution of

the unknown salt. This will result in the precipitation of the sulphate as barium sulphate.

BaCl2(aq) + M2SO4(aq) →BaSO4(s) + 2 MCl(aq) (assuming +1 cation)

BaCl2(aq) + MSO4(aq) →BaSO4(s) + MCl2(aq) (assuming +2 cation)

The barium sulphate precipitate is collected by filtration, ignited and weighed. The number of

moles of sulphate can be determined from the mass of the barium sulphate. Since barium

chloride is added in excess, and since the precipitation reaction is assumed to go to completion,

the number of moles of sulphate recovered in the precipitate can be assumed to be equal to the

number of moles of sulphate in the original sample allowing for the calculation of the percentage

by mass of sulphate in the original sample.

In order to obtain the best results the BaSO4 crystals should be as large as possible. This

facilitates filtration and washing of the crystals and the decreased surface area minimizes the

amount of impurities adsorbed onto the crystals. Generally the largest crystals are obtained when

the rate of precipitation is as low as possible. The rate of precipitation is minimized by slowly

adding the BaCl2 solution to the aqueous mixture containing the unknown salt while

continuously stirring the mixture. The rate of precipitation can be decreased still farther by

slightly increasing the solubility of the BaSO4 (remember that a substance that is said to be

insoluble is in fact very slightly soluble). The increase in solubility is achieved by lowering the
pH with the conc. HCl and by increasing the temperature. The resulting decrease in the yield of

the BaSO4 is insignificant.

THEORETICAL PRINCIPLE

Gravimetric methods are quantitative methods that are based on determining the mass of

a pure compound to which the analyte is chemically related. Gravimetric methods are concerned

with the determination of a substance by the process of weighing. If an element or radical is to be

determined and it is first converted into a stable compound of a known composition and the mass

of the compound is determined accurately. From this information the mass of element or radical

can be calculated. It can be therefore said that gravimetric analysis involves precipitation,

filtration, washing of the precipitate and drying, ignition and weighing of the precipitate. 

The steps commonly followed in gravimetric analysis are:

 Preparation of a solution containing a known weight of the sample.

 Separation of the desired constituent.

 Weighing the isolated constituent.

 Computation of the amount of the particular constituent in the sample from the

observed weight of the isolated substance.

  Because of the nature of the laboratory experience the area in which we will focus on it

Precipitation Gravimetry. This requires that the substance to be weighed be readily removed by

filtration. In order for a precipitate that cannot be filtered to form, it must be supersaturated with

respect to its solubility product constant. However, if it is too far above the saturation limit,

crystal nucleation may occur at a rate faster than crystal growth i.e. the addition of molecules to a

crystal nucleus, eventually forming a crystal that cannot be filtered. When this occurs, numerous

tiny micro-crystals are formed rather than a few large ones. In the extreme case, micro-crystals
may behave as colloids and pass through a fibrous filter. To avoid this, precipitating solutions

may be heated. Because the solubility of most salts increases with increasing temperature, this

treatment will lower the relative degree of super saturation and slow the rate of nucleation. Also,

one might add the precipitant slowly with rapid mixing to avoid the occurrence of locally high

concentrations.

Precipitation gravimetry is often practiced at high ionic strengths. This is to reduce the

electric double layer thickness (salting-out effect) of the slowly forming crystals. When this

occurs, electrostatic repulsion between the crystal and its precipitating molecules is reduced.

Crystal growth can then occur more rapidly. It is very important that the precipitate be pure and

has the correct

PROCEDURE

As per lab handout with the following deviation:

- The sample was pre-died in an oven at 105 oC for at least two hours (step 1).

- The sample was weighed in a piece of paper instead of a 500mL beaker (step 1).
RESULTS

Group Sample Mass Data Mean % ( SO 24) % MgSO4

1 0.619 0.568 0.56 0.567 0.567

7 37.69937 47.25177
2 0.502 0.497 0.49 0.488 0.492

1 40.33696 50.55767
3 0.629 0.546 0.54 0.541 0.544

4 35.59508 44.61428
4 0.500 0.382 0.38 0.372 0.379

2 31.19686 39.10163
5 0.503 0.398 0.39 0.398 0.398

8 32.56543 40.81697
6 0.509 0.263 0.26 0.262 0.263

4 21.2657 26.65407
7 0.534 2.483 2.48 2.484 2.484

4 191.4485 239.9584
8 0.558 0.554 0.55 0.554 0.554

4 40.86178 51.21547

Table 1 showing the collection of raw data after the experiment along with the calculated

means and percent sulphate

Before the total mean or any other statistical analysis could be performed, the q test was done to

on the value 2.484 to identify if the value is an outlier and should be removed from the data set.

Results of the Q test:

Qc > Qt

0.863 > 0.41

Since Qc is more than Qt (at 90% CL), this therefore means that the value 0.863 is an outlier and

cannot be used in the data set. This therefore means that it will not be used in the statistical

analysis of the pooled data.

Data
Total Mean 0.457
Total Mean % SO 4
2
53.9
Total Mean % MgSO4 67.5
Standard Deviation 0.349
Confidence Interval 0.3882<µ<0.7928

Group Data Sample Mean Standard Deviation Confidence Interval % ( SO 24)

Mass
0.546 0.629 0.544 0.0025 2.480<µ<2.488
0.544 36.2
0.541
Table 2 showing the results from the required calculations

Table 3 represents our group data after completing the experiment. (Calculations shown in

detail in the appendix)

DISCUSSION

In the experiment, sample containing some sort of sulphate was dried, weighed and

dissolved in HCl. After, barium chloride was added which resulted in the formation of barium

sulphate precipitate. The precipitation reaction is:

Ba2+ (aq) + SO42- (aq) ---> BaSO4 (s)

After, the solution was digested in a steam bath, filtered and washed. It was noticed that

the solution became cloudy after AgNO3 was added. This is because AgNO3 acted as a test for

residual chloride. This means that after washing, some amount of precipitate was present in the

filtrate. Therefore, the precipitate had to be washed and tested until the filtrate remained clear.

The filter containing the precipitate was then transferred to the crucible for drying and

ignition. This was a time consuming process as the filter paper in the crucible must be

completely dry for faster burning. After the paper was completely charred and only the

precipitate remained in the crucible, it was transferred into the desiccator. The desiccator

contains silica gel beads that remove water from the precipitate. It also helps to block out

moisture. It is therefore important to transfer the crucible immediately to the desiccator so it

would not be subject to moisture.

 There were many factors which affected the filterability of the barium sulphate

precipitate. This includes variations in acidity and temperature. Also, the filterability can be

affected by the manner in which barium chloride was added, how constant the solution was

stirred and the extent to which the foreign ions are co-precipitated. These foreign ions include

nitrate, chlorate and chloride. The co-precipitation of chloride can be decreased by slow addition

of the precipitate and rapid stirring (Seely, 2010).

One error that occurred was random error. The crucibles used in this experiment were all

placed in the same desiccator. Though, attempts were made to mark the desiccators, there was

still uncertainty as to whether the crucible used for charring is the same used for weighing. Every

crucible does not have the same weight; hence this could be a factor affecting the experiment.

One way of minimizing error is by using ashless filter paper. To get the mass of the

residue, the filter paper must often be combusted. If the filter paper contains ash, the ash will

remain behind thereby contaminating the sample and changing the weight of the precipitate. By

using ashless filter paper, contamination is avoided and proper mass measurements are

promoted.

CONCLUSION

In conclusion, the percentage sulphate in the precipitate is 36.2% and for the pooled data was

45.4%.

REFERENCES
 1) HAGE, S. and CARR, D. (2011) Analytical chemistry and quantitative analysis. New

Jersey: Pearson Prentice Hall.

2) SKOOG, D… [et al] (2013) Fundamentals of Analytical Chemistry. 9th Edition. Cengage

Learning.

3) Holler, F. James; Skoog, Douglas A.; West, Donald M. (1996). Fundamentals of

analytical chemistry. Philadelphia: Saunders College Pub. ISBN 0-03-005938-0.

APPENDICES

The equations used below were used to calculate the mean, standard deviation and confidence

interval and to determine the percentage of Iron in the precipitate Iron (iii) Oxide.

Q Test

Questionable Value−Nearest Value

QC =
Range

2.484−0.567
QC =
2.484−0.263

1.917
QC =
2.221

QC = 0.863

Qc > Qt

0.863 > 0.41

 Since Qc is more than Qt (at 90% CL), this therefore means that the value 0.863 is an

outlier and cannot be used in the data set.

Mean

Mean ( x ) =
∑ of DataValues
Number of Samples (n)

0.546+0.544+ 0.541
Mean ( x ) =
3

Mean ( x ) = 0.544

The mean for the pooled data can be found in a similar manner.

Standard Deviation

x 1= 0.544

S1 = √ ε ¿ ¿ ¿

S1 = √(0.546 – 0.544)2 +¿ ¿ ¿

S1 = √ ¿ ¿ ¿

S1 =
√ 0.000013
2

S1 = √ 0.0000065

S1 = 0.0025
 The Standard deviation for my group (S1) is therefore 0.0025. The Standard deviation for

the pooled data (S2) can be found in a similar manner as S1.

Confidence Interval

t (at 90% CL)= 2.920

S1 = 0.0025

ts
x±
√n

2.920× 0.0025
0.544 ±
√3

0.0073
2.484 ±
1.732050808

2.484 ± 0.0042

2.480<µ<2.488

The Confidence Interval for my group (CI1) is therefore 2.480<µ<2.488. The Confidence

Interval for the pooled data (CL2) can be found in a similar manner as CL1.

% of sulphate

The mass of the weighted epson salt = 0.629g

Therefore number of moles of the precipitate:

0.544 g ( 233.4
1 mol
g)
−3
=2.37 ×10 mol

Given the 1:1 ratio, there are also 2. 37 ×10−3 mol of sulphate ions in the precipitate.
Calculated the mass of the sulphate ions in the precipitate:

2.37 ×10−3 mol ( 96.06

1 mol )
g
=0.228

Calculated the theoretical percentage of sulphate content in the sulphate sample:

( 0.228
0.629 )
. 100 %=36.2%

% of MgSO4

Now from the assumption that is MgSO4, the % MgSO4 is calculated as such:

Therefore number of moles of the precipitate:

Assuming all the sulphate in the sample is in the form of magnesium sulphate.The equation, as

stated before has 1:1 mole ratio. So number of moles is

2.37 ×10−3 mol

Calculating mass of MgSO4

−3
2.37 ×10 mol ( 120.4
1 mol )
g
=0.285 g

Calculated the theoretical percentage of sulphate content in the sulphate sample:

( 0.285
0.629 )
. 100 %=45.4 %