Experiment

Gravimetric Analysis of a Chloride Salt

To illustrate typical techniques used in gravimetric analysis by quantitatively determining the amount of chloride in an unknown. Apparatus balance 250-mL beakers (6) Bunsen burner funnels (3) funnel support plastic wash bottle graduated cylinders (2), 10 and lOOmL Chemicals unknown chloride sample O.SM AgN03 6MHN03

OBJECTIVE APPARATUS AND CHEMICALS

ring stand, ring, and wire gauze stirring rods (3) rubber policeman (3) sharkskin filter paper (3) watch glasses (3) weighing paper

acetone distilled water

Quantitative analysis is that aspect of analytical chemistry concerned with determining how much of one or more constituents is present in a particular sample of material. Information such as percentage composition is essential to establishing formulas for compounds. Two common quantitative methods used in analytical chemistry are gravimetric and volumetric analysis. Gravimetric analysis derives its name from the fact that the constituent being determined can be isolated in some weighable form. Volumetric analysis, on the other hand, derives its name from the fact that the method used to determine the amount of a constituent involves measuring the volume of a reagent. Usually, gravimetric analyses involve the following steps:
1.

DISCUSSION

2. 3. 4. 5. 6. 7.

Drying and then accurately weighing representative samples of the material to be analyzed. Dissolving the samples. Precipitating the constituent in the form of a substance of known composition by adding a suitable reagent. Isolating the precipitate by filtration. Washing the precipitate to free it of contaminants. Drying the precipitate to a constant mass (to obtain an analytically weighable form of known composition). Calculating the percentage of the desired constituent from the masses of the sample and precipitate.

From Laboraton; Experiments, Tenth Edition, John H. Nelson and Kenneth C. Kemp. Copyright 2006 by Pearson Education, Inc. Published by Prentice Hall, Inc. All rights reserved.

11

Gravimetric Analysis of a Chloride Salt

Although the techniques of gravimetric analysis are applicable to a large variety of substances, we have chosen to illustrate them with an analysis that incorporates a number of other techniques as well. Chloride ion may be quantitatively precipitated from solution by the addition of silver ion according to the following ionic equation: Ag+(aq) + Cqaq) ~ AgCl(s)
[1]

Silver chloride is quite insoluble (only about 0.0001 g of Agel dissolves in 100 mL of H 20 at 20C); hence, the addition of silver nitrate solution to an aqueous solution containing chloride ion precipitates Agel quantitatively. The precipitate can be collected on a filter paper, dried, and weighed. From the mass of the Agel obtained, the amount of chloride in the original sample can then be calculated. This experiment also illustrates the concept of stoichiometry. Stoichiometry is the determination of the proportions in which chemical elements combine and the mass relations in any chemical reaction. In this experiment stoichiometry means specifically the mole ratio of the substances entering into and resulting from the combination of Ag+ and el- . In the reaction of Ag+ and el- in Equation [1], it can be seen that 1 mol of chloride ions reacts with 1 mol of silver ions to produce 1 mol of silver chloride. Thus, moles el- = moles Agel = grams Agel , I l f mo ar mass o Agel

grams Cl in sample = (moles cn(gram-atomic weight Cl) (gram-atomic weight Cl)(grams Agel) molar mass of Agel (35.45 g Cl)(grams Agel) 143.32 g Agel

~ gC ljg gCl)(grams Agel)

The number 0.2473 is called a gravimetric factor. It converts grams of Agel into grams of Cl. Gravimetric factors are used repeatedly in analytical chemistry and are tabulated in handbooks. The percentage of Cl in the sample can be calculated according to the following formula:
% Cl m sample = ...:.:::.._ _ _ _ __.:..___:.....:_____:.

(grams Cl in sample)(lOO) gram-weight sample

EXAMPLE

<;;_

In a gravimetric chloride analysis it was found that 0.2516 g AgCl was obtained from an unknown that had a mass of 0.1567 g. What is the percent of chloride in this sample?

'\J

SOLUTION: The mass of Cl in the sample is: g Cl = (0.2473 g Clfg AgCl)

= 0.06222 g Cl
X

(0.2516 g AgCl)

(0.06222 g Cl)(lOO) % Cl = --:-:-----'=---.,-,(0.1567 g sample)

39.72%

12

Gravimetric Analysis of a Chloride Salt

Obtain an unknown and record its number on your report sheet. On a piece of weighing paper, weigh to the nearest 0.0001 g about 0.2 to 0.4 g of your unknown sample. Transfer the sample quantitatively to a clean 250-mL beaker (do not weigh the beaker) and label the beaker #1 with a pencil. Record the sample weight. Add 150 mL of distilled water and 1 mL of 6 M HN0 3 to the beaker. Repeat with sample numbers 2 and 3, and label the beakers #2 and #3, respectively. Using a different glass rod for each solution, stir until all of the sample has dissolved. Leave the stirring rods in the beakers. Do not place them on the desktop. While stirring one of the solutions, add to it about 20 mL of 0.5 M AgN0 3 solution. Place a watch glass over the beaker. Warm the solution gently with your Bunsen burner and keep it warm for 5 to 10 min. Do not boil the solution. Obtain a filter paper (three of these will be needed) and weigh it accurately. (Be certain that you weigh the paper after it has been folded and tom, not before.) Fold the paper as illustrated in Figure 1 and fit it into a glass funnel. Be certain that you open the filter paper in the funnel so that one side has three pieces and one side has one piece of paper against the funnel-not two pieces on each side. Why? Your instructor will also demonstrate this for you. Wet the paper with distilled water to hold it in place in the funnel. Completely and quantitatively transfer the precipitate and all the warm solution from the beaker onto the filter, using a rubber policeman (your laboratory instructor will show you how to use a rubber policeman) and a wash bottle to

PROCEDURE

Fold and crease lightly.

;-f'\. ----~-<~
Tea r off corner unequally. Open out to form a cone with one piece of paper against one side and three pieces of paper against the other side of the funnel.

Seal the moistened edge of the filter paper against the funnel, making sure that the paper over the bottom portion is set firmly aga inst the funnel to prevent air from being sucked down the side of the paper.

Pour down a glass rod to aid in transfer.

The filtrate should run down the walls of the beaker. The weight of the water column hastens filtration. Use a rubber policeman to transfer the last traces of precipitate from the bea ker.

A FIGURE 1 Filter paper use.

13

Gravimetric Analysis of a Chloride Salt

wash out the last traces of precipitate. The level of solution in the filter funnel should always be below the top edge of the filter paper. Wash the precipitate on the filter paper with two or three 5-mL portions of water from the wash bottle. Finally, pour three 5-mL portions of acetone through the filter. (CAUTION: Acetone is highly flammable! Keep it away from open flames.) Remove the filter paper, place it on a numbered watch glass, and store it in your locker until the next period. Repeat the above processes with your other two samples, being sure that you have numbered your watch glasses so that you can identify the samples. The precipitated AgCl must be kept out of bright light, because it is photosensitive and slowly decomposes in the presence of light as follows: 2AgCl(s)
lzv
-----+

2Ag(s)

+ Cl2(g)

In this equation hv is a symbol for electromagnetic radiation; here it represents radiation in the visible and ultraviolet regions of the spectrum. This is the reaction used by Corning to make photosensitive sunglasses. In the next period, when the AgCl is thoroughly dry, weigh the filter papers plus AgCl and calculate the mass of AgCl. From these data calculate the percentage of chloride in your original sample.

Standard Deviation
As a means of estimating the precision of your results, it is desirable to calculate the standard deviation. Before we illustrate how to do this, however, we will define some of the terms above as well as some additional ones that are necessary.

Accuracy: correctness of a measurement, closeness to the true result. Precision: internal consistency among one's own results-that is, reproducibility.

Error: difference between the true result and the determined result. Determinate errors: errors in method or performance that can be discovered and eliminated.

Indeterminate errors: random errors, which are incapable of discovery but

which can be treated by statistics.

Mean: arithmetic mean or average (J.t), where J.t=

sum of results number of results

For example, if an experiment's results are 1, 3, and 5, then

J.t=

+3+5
3

=3

Median: the midpoint of the results for an odd number of results and the
average of the two middle results for an even number of results (m). For example, if an experiment's results are 1, 3, and 5, then m = 3. If results are 1.0, 3.0, 4.0, and 5.0, then m
=

3.0

+ 4.0
2

35 .

14

Gravimetric Analysis of a Chloride Salt

The scatter about the mean or median-that is, the deviations from the mean or median-are measures of precision. Thus the smaller the deviations, the more precise the measurements.
EXAMPLE

If an experiment's results are 1.0, 2.0, 3.0, and 4.0, calculate the mean, the deviations from the mean, the average deviation from the mean, and the relative average deviation from the mean. SOLUTION: The mean is calculated as follows:
J.L =

1.0

+ 2.0 + 3.0 + 4.0

4

=- =

10.0 4

2.5

The deviations from the mean are 12.5 - 1.01 = 1.5 12.5 - 2.01 = 0.5 12.5 - 3.01 = 0.5 12.5 - 4.01

= 1.5

The symbol I I means absolute value, so all differences are positive. The average deviation from the mean is therefore 1.5

+ 0.5 + 0.5 + 1.5

4

1.0

The relative average deviation from the mean is calculated by dividing the average deviation from the mean by the mean. Thus Relative deviation

2.5

l.O

= 0.40

This can be expressed as 40%, 400 parts/ thousand (ppt), or 40,000 parts/ million (ppm).

EXAMPLE

If an experiment's results are 1.0, 1.5, 2.0, and 2.5, calculate the mean, the deviations from the mean, the average deviation from the mean, and the relative average deviation from the mean.

SOLUTION: The mean is calculated as follows: 1.0

J.L =

+ 1.5 + 2.0 + 2.5

4

. = 4 = 1.75 , or 1.8 to two stgnificant f tgures The deviations from the mean are 11.8 - 1.01 = 0.8 11.8 - 1.51 = 0.3 11.8 - 2.01 = 0.2 11.8 - 2.51

70

= 0.7

15

Gravimetric Analysis of a Chloride Salt The average deviation from the mean is therefore

_0._8_+_0_.3_+____:.0_ .2_+____:.0_ = 0 5 .7

The relative average deviation from the mean is

o.s
1.8

0.3

= 30%, or 300 ppt, or 30,000 ppm

Obviously, the data in Example 3 are internally more consistent than the data in Example 2 and hence are more precise, since the deviations are smaller. Thus, the average deviation and relative average deviation measure precision. Standard deviation (s) is a better measure of precision and is calculated using the formula

sum of the squares of the deviations from the mean number of observations - 1

where s = standard deviation from the mean, Xi = members of the set, p, = mean, and N = number of members in the set of data. The symbol 2:i means to sum over the members.
EXAMPLE 4 An experiment's results are 1, 3, and 5. Calculate the mean, the deviations from the mean, the standard deviation, and the relative standard deviation for the data. SOLUTION: The mean is as follows:
f.L =

1+3+5 =3 3

The deviations from the mean are

lx; - JLI

= = =

deviation 2 0

ll- 31 13- 31 Is - 31

= 2 s = /r"2-+ 02,-----+- 2"2 2 -----,

'Y
=

3- 1

)4 + ~ + 4

16

Gravimetric Analysis of a Chloride Salt

The results of this experiment could be reported as 3 2. The relative standard deviation is

"3 = 0.7, or 70%

EXAMPLE 5 The results of an experiment are 2.100, 2.110, and 2.105. Calculate the mean, the deviations from the mean, the standard deviation, and the relative standard deviation.

SOLUTION: The mean is as follows.

JL =

2.100

+ 2.110 + 2.105
3

2105 .

The deviations from the mean are:

12.105 - 2.1001 = 0.005 12.105 - 2.1101 = 0.005 1 2.105 - 2.1051 = 0.000

The standard deviation is therefore: s

=

(0.005) 2

+ (0.005) 2 + (0.000) 2
2

=
=

)5

X 10- S 2

0.005

The results could be reported as 2.105 0.005. The relative standard deviation is
0.005 = 0.002 or 0.2% - 2 .105

Obviously, the data in Example 5 are more precise, though not necessarily more accurate, than the data in Example 4, because both the deviations and the standard deviation are smaller in Example 5. Calculate the standard deviation of your data and report the results on your report sheet. The standard deviation may be used to determine whether a result should be retained or discarded. As a rule of thumb, you may discard any result that is more than two standard deviations from the mean. For example, if you had a result of 49.65% and you had determined that your percentage of chloride was 49.25 0.09%, this result (49.65%) could be discarded. This is because s = 0.09 and 149.25 - 49.651 = 0.40, which is greater than 2 X 0.09. This result is more than two standard deviations from the mean. Before beginning this experiment in the laboratory, you should be able to answer the following questions:
1.

PRE LAB

QUESTIONS

What is the fundamental difference between gravimetric and volumetric analysis? What does stoichiometry mean?

2.

17

Gravimetric Analysis of a Chloride Salt

3. 4. 5. 6. 7. 8.

Why should silver chloride be protected from light? Will your result be high or low if you don't protect your silver chloride from light? Can you eliminate indeterminate errors from your experiment? Does standard deviation give a measure of accuracy or precision? Why don't you open your folded filter paper so that two pieces touch each side of the funnel?
If your silver chloride undergoes extensive photodecomposition before you weigh it, will your results be high or low? If an experiment's results are 10.1, 10.4, and 10.6, find the mean, the average deviation from the mean, the standard deviation from the mean, and the relative deviation from the mean.

9.

What is meant by the term gravimetric factor?

18