Chloride determination of an unknown sample by gravimetric analysis

Sarah Uddin

Lab partners Rosio and Pierre

Dates performed: 1/30/2017, 2/1/2017, 2/6/2017, 2/8/2017, 2/15/2017

Date due: 2/22/2017

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Introduction:

Gravimetric analysis is a process often used to determine the mass percent of an ion in an

unknown salt. Determination is made by comparing the mass of two compounds, both containing

the ion being analyzed, the analyte1.

During gravimetric analysis, the unknown salt is dissolved and a solution containing an

ion which reacts with the aqueous analyte is added to form a solid, pure precipitate with a known

molecular weight. This known precipitates mass determines the mass of analyte present in the

solution. This mass is then compared to the initial mass of the unknown sample to determine

percent of analyte it contains.

Since the unknown sample can absorb moisture from air exposure, the sample is dried. If

mass is obtained prior to drying, initial mass will include impurities in the salt and result in a low

percent mass.

In chloride determination by gravimetric analysis, AgNO3 is often used to precipitate

AgCl, see the following equations 1 and 2:

AgNO3 (s) Ag+(aq) + NO3-(aq) eq. 1

Ag+(aq) + Cl-(aq) AgCl (s) eq. 2

Attention to factors which affect the final mass of AgCl is of primary importance.

Specifically, colloidal precipitate formation, coprecipitates, common ions contamination, and pH

fluctuation, and the photodecomposition of silver compounds need to be considered to ensure a

true and accurate AgCl mass is obtained.

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Slowly adding the

AgNO3 solution to just

excess concentration is

important to prevent

suspended colloids in

supersaturated conditions2.

When aqueous ions come

together to form salts, there

are two separate processes:

Figure 1
nucleation, the initial ionic bonding of small aggregates of ions, then particle growth, which

adds more molecules to that nucleus, to form a larger crystal2. See figure 1a. In supersaturated

solution, nucleation occurs faster than particle growth, resulting in small suspended colloids,

which pass easily through filters, resulting in loss of the analyte. See figure 1b. By adding the

AgNO3 slowly, while mixing vigorously, in dilute conditions helps prevent this loss of analyte2.

Also, digestion, or standing in heated solution, allows crystal size to increase because the salt

slowly recrystallizes, promoting particle growth.

An electrolytic solution is ideal for formation of salt solids. The increased ions in the

solution lowers the kinetic energy required for ions to react through the adsorption layers

surrounding the crystal in solution2. HNO3 is added to the solution with the dissolved unknown

salt to maintain electrolyte concentration. This also lowers pH which is beneficial to prevent

coprecipitation of AgOH, by the following equation:

Ag+(aq) + OH-(aq) AgOH (s) eq. 3

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Though the electrolyte solution is ideal for salt formation, alternate ions present results in

coprecipitations. Both adsorbed, surface bonded, and occluded, internal coprecipitation, are

possible2,3. See equations 4 and 5 for possible coprecipitates formed, even if solubility constants

are not met2. Equation 5 accounts for dissolved CO2 (g) from the air.

2Ag+(aq) + NO3-(aq) + Cl-(aq) AgNO3 (s) + AgCl (s) eq. 4

CO2 (g) + 2H2O (l) + 2Ag+(aq) + Cl-(aq) H3O+(aq) + HCO3-(aq) + 2Ag+(aq) + Cl-(aq)

AgHCO3 (s) + AgCl (s) eq. 5

Adsorbed and/or occluded silver ions can also be present. Washing the precipitate with a

gathering agent, like dilute HNO3 solution, removes coprecipitates, like silver nitrate and silver

bicarbonate, and silver ions. The dilute HNO3 wash also maintains electrolyte concentration and

prevents breaking down, or peptization, of the AgCl, by resolubilizing the AgCl when

washing2,3. Peptization results in loss of analyte.

Another loss of analyte occurs during photodecomposition of AgCl from UV light

exposure. Photodecomposition results in reduction of silver ions and oxidation of chloride ions to

form solid silver and gaseous chlorine, see equation 63. Therefore, limiting light exposure to the

product, AgCl, is important.

2AgCl (s) + hv 2Ag (s) + Cl2 (g) eq. 6

In this experiment, an unknown salt sample containing chloride was dissolved in a dilute

HNO3 solution. AgCl was precipitated by an AgNO3 solution, heated to digest, then filtered in a

purified/dry crucible. The AgCl precipitate was washed with a diluted HNO3 solution, then dried.

The mass of AgCl was used to determine the percent mass of chloride in the unknown sample.
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Results:
Table 1: Gravimetric results after precipitating Cl- with AgNO3

Sample Mass Unknown Mass Crucible Mass Crucible Mass AgCl

(g) (g) and AgCl (g) (g)

1 0.5420 (.0001) 29.5337 (.0001) 30.7529 (.0001) 1.2192 (.0001)

2 0.5066 (.0001) 30.5641 (.0001) 31.6887 (.0001) 1.1246 (.0001)

3 0.5054 (.0001) 29.6612 (.0001) 30.8108 (.0001) 1.1496 (.0001)

Result Calculations:

Sample 1
1 1 35.45
1.2192 (.0001)
143.32 1 1
1
= 0.3016 100% = . %
. 5420 (.0001)
Sample 2
1 1 35.45
1.1246 (.0001)
143.32 1 1
1
= 0.2782 100% = . %
. 5066 (.0001)
Sample 3
1 1 35.45
1.1496 (.0001)
143.32 1 1
1
= 0.2843 100% = . %
. 5054 (.0001)

Average Percent Chloride:

55.64+54.91+56.26
3
= . . %
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Statistical Analysis Calculations:

Propagation of error for Gravimetric analysis:

. 0001 2 . 0001 2 . 0001 2

( ) +( ) + ( ) = = .01075 = .
. 5173 29.9197 31.0841 55.60

95% Confidence interval for Gravimetric Method:

4.303 .6757
= 1.679 = %
3
95% Confidence interval for Fajans method:
4.303 1.207
= 2.999 = %
3

T-test to compare true value to Fajans method mean:

3
= (56.5 56.7) = .2862 < 4.303
1.21
There is 95% confidence that Fajans method is producing results close to true value.

T-test to compare true value to gravimetric method mean:

3
= (55.6 56.7) = 2.857 < 4.303
. 667
There is 95% confidence that gravimetric analysis is producing results close to true value.

Q Test for Fajans method:

|57.76 56.43|
= .550 < .970 95%
57.76 55.34
57.76 is not an outlier.

Q Test for Gravimetric analysis:

|54.91 55.64|
= .541 < .970 95%
56.26 54.91
54.91 is not an outlier.
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Comparison of Fajans Method and Gravimetric Analysis of the same unknown sample:

Table 2: Comparison of Fajans and Gravimetric method:

N Fajans Method, % Cl- N Gravimetric Analysis, % Cl-

1 57.75 1 55.64
2 56.43 2 54.91
3 55.34 3 56.26
Mean 56.51 Mean 55.60
Standard Deviation 1.21 = 1 Standard deviation .677 = .7
Relative SD .0214 = .02 Relative SD .0122= .01
Absolute Error -.19 =-.2 Absolute Error -1.1 =-1
Relative Error% -.335= -.3% Relative Error% -1.94 = -2%
Confidence interval 56 3 % Confidence Interval 56 2 %
Propagation of error .2 Propagation of error .01

T- test to compare values obtained by Fajans and Gravimetric method:

1.2072 (3 1) + . 67572 (3 1)
= .9781 =
(3 + 3 2)

|56.51 55.60| 3 3
= 1.139 =
. 9781 3+3

95% , 4 , = 2.776
1.139 < 2.776
There is 95% confidence that the fajans method and gravimetric analysis produced the same
value for this sample.

F test to compare precision between gravimetric and fajans method:

1.212
= 3.204 < 9.28
. 6762
No significant difference in precision between Fajans and gravimetric method for these
values.
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Discussion:

After performing gravimetric analysis on an unknown salt containing chloride ions by

addition of silver nitrate solution, 55.60% (w/w) chloride determination was measured. This

methods mean was statistically proven to be significantly similar to true value of 56.70% (w/w)

with 95% confidence.

However, the relative error of -2% reflects a loss of product occurred in the process of

precipitating, washing, drying and/or weighing the silver chloride. The mass of crucible, with

and without AgCl, was dried to a constant mass within .2mg, so it is unlikely a high source of

error occurred while drying or weighing the product. Therefore, it is more likely error was

introduced in the process of precipitating and washing the AgCl.

The rate in which the silver nitrate solution was added to the dissolved unknown salt was

faster than ideal for particle growth of AgCl. It is possible nucleated suspended colloidal

precipitates formed during the rapid addition of silver nitrate solution. The suspended colloidal

precipitates form hydration shells and/or adsorbance layers of excess silver ions and might not

have aggregated to form larger crystals during the two day digestion period in which the

precipitate was kept in the reaction flask prior to washing. These suspended colloidal precipitates

would not have formed large enough particles to be retained during the washing process,

resulting in loss of AgCl.

Another source of error was introduced by light exposure which occurred during the

precipitating and washing of AgCl. This caused a color change of the AgCl from white to a pale,

light purple. This photodecomposition, evident from the color change, caused some chloride ions

to be lost as chlorine gas, contributing to the -2% relative error. Also, though a dilute electrolyte
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solution of HNO3 was used to wash the AgCl, it is still possible peptidization occurred during

this process, causing loss of AgCl.

Other possible sources of error may have produced a larger than true mass measurement

of AgCl, which would then make the errors discussed above more pronounced as the net

negative relative error reveals a loss of product. These errors include possible coprecipitates of

AgHCO3 and AgNO3 which, if occluded, would have not been gathered by washing with dilute

HNO3 solution. Since the pH was kept constant, it is unlikely AgOH coprecipitated in solution.

If the above coprecipitates did form, errors which resulted in the loss of product which

contributed to the -2% relative error would be more drastic than currently thought.

In Fajans method, a standard solution of NaCl and dichlorofluorescein indicator (DCF)

was titrated to determine the exact concentration of silver nitrate solution. This silver nitrate

solution was then used to titrate the dissolved unknown and DCF to determine the mass percent

of chloride as 56.51%(w/w). This produced a small relative error of -.3%. Possible errors include

drying and weighing the NaCl standard and unknown salt, and inaccurate titration with silver

nitrate solution.

Though the standard NaCl was dried, it was not dried to constant mass. If the NaCl was

impure when weighed by difference for the standard NaCl solution, the true molarity of silver

nitrate solution determined would have been inaccurate. If the unknown was not dried fully

before weighed by difference, the percent chloride determination would be inaccurate, as well.

It is also possible the equivalence point of titration was not detected immediately because

the color change to faint pink was difficult to discern when temporary. Therefore, if not detected,

a larger volume of silver nitrate could have been measured than was actually needed, resulting in
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an inaccurate percent mass determination. These errors could explain the 1 percent chloride

standard deviation in the Fajans method, as well.

Absolute errors in glassware and physical limitation of scales occurred in both the

gravimetric and Fajans method. However, when propagating error, the standardization of the

silver nitrate solution, the absolute error of transfer pipets and burets needed to be accounted for

in Fajans method, allowing the final mass determination to be 56.5 .2% (w/w). The gravimetric

analysis error propagation only accounted for the masses of unknown and precipitated product,

allowing the final mass determination to be 55.30 .01% (w/w).

When comparing the gravimetric method of chloride percent mass determination to

Fajans method recently performed, statistical analysis shows that the gravimetric method

produced a less accurate measurement with -2% relative error compared to Fajans -0.3%

relative error. However, gravimetric method was more precise, producing a standard deviation of

0.7 to Fajans 1. For full comparison, see table 2.

However, these differences in both precision and accuracy were found to be statistically

irrelevant as there is 95% confidence that the gravimetric method and Fajans method produced

values similar to the true value, that the values produced by both methods were similar to one

another, and that there was no significant different in the precision between the two methods.

However, in the absence of systematic error, such as the rapid addition of silver nitrate

solution which occurred during the gravimetric analysis, the gravimetric analysis could prove to

be both more accurate and more precise. This conclusion is supported by the calculated

propagation of error, which was far lower in gravimetric analysis, indicating a greater degree of

certainty in the measurements produced. Therefore, the gravimetric method would be the better
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choice for determination of mass percent of an analyte in an unknown salt. Therefore, if given

the task to analyze a series of samples, it may prove to be beneficial to use gravimetric method

over the Fajans method.

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References

1. Wired Chemist. Gravimetric Analysis. http://www.wiredchemist.com/chemistry/

instructional/laboratory-tutorials/gravimetric-analysis (accessed Feb 1, 2017).

2. Harris, D. C. Quantitative chemical analysis, 7th ed.; W.H. Freeman: New York, NY,

2007.

3. Skoog, D. A. In Fundamentals of Analytical Chemistry; Cengage Learning: Boston, MA;

pp 814815.