Experiment 1 and 2: Determination of Chloride

Concentration in Water by Gravimetric Methods and

Precipitation Titration
Chem 374 Analytical Chemistry Laboratory

Principle and Background

The vast majority of water sources such s groundwater and rainfall contain chloride, a mobile

anion. Due to the plethora of chloride in various natural water sources, several methods of analysis for the

determination of chloride are utilized. In these experiments, two methods are employed and compared in

the analysis of the content of chloride in water. These two methods for the determination of chloride are

by gravimetric methods and precipitation titration.

In precipitation methods, “the analyte is converted to a slightly soluble precipitate which is

filtered, washed free of impurities, and converted to a product of known composition by suitable heat

treatment.” The product is weighed and then analyte content of the sample is then determined through

stoichiometry. The mass of the sample and the mass of a product of known composition are necessary in

order to compute the results of a gravimetric analysis. If the product is the analyte, the concentration is
 1

found as a percentage of the analyte by taking the ratio of the mass of analyte to the mass of sample. A

product that is not the analyte is multiplied by the gravimetric factor (GF) which accounts for the

stoichiometric relationship between the analyte and product weighed. Selective reagents react with a

narrow amount of species so that a product with a high purity, low solubility, unreactive nature, and high

molar mass is obtained. Gravimetric methods are absolute meaning that they don’t require any form of

calibration, requiring a shorter amount of operator time per sample. Sensitivity and accuracy are typically

dependent on the type of analytical instrument that is utilized. The chloride content of water can be

determined by the precipitation of the anion as AgCl (s). The precipitate is collected in a weighed

crucible, that is washed, and then dried to determine its mass. The solution is held somewhat acidic to

eliminate any interference from anions of weak acids that may produce a soluble salt in a neutral medium.

Excess silver ion is necessary to reduce the solubility of AgCl, but should also be avoided to prevent

coprecipitation of silver nitrate. AgCl is initially formed as a colloid and then coagulated with heat. This

coagulation is promoted by nitric acid and excess silver nitrate in order to provide a high electrolyte

concentration. Nitric acid maintains this electrolyte concentration, and eliminates any possible peptization

during washing.

Titrimetric methods of analysis make up a large group of quantitative procedures. A measured

quantity is equivalent to the volume of a standard solutions needed to react completely with the analyte.

Neutralization titrations are primarily used for determining the concentrations of analytes that are

acids/bases or convertible to a species by an acceptable treatment. These concentrations are expressed in

molarity (M), which provides the number of moles of a reagent in a L of solution. An equivalent is a

compound that can product a mole of positive or negative charge, but an amount of a substance in an

equivalent varies from reaction reaction. The equivalence point of a titration is reached when the amount

of an added titration is chemically equivalent to the amount of analyte within a sample. This experiment

utilises a Mohr titration, which reaches its equivalence point through the presence of chromate which

forms a reddish-orange Ag2CrO4 precipitate after most of the chloride has precipitated. The pH is
 2

buffered within a range of 7-10 as the chromate is converted to dichromate Cr2O72-, a soluble salt

at a lower pH. At pH greater than 10, Ag2O may precipitate, forming an upper pH limit for all

argentometric titrations. Silver chromate precipitation will ideally start at the equivalence point

2−¿
Cr O¿4 =¿
of silver chloride titration, [Ag+] = √❑ . The solubility of Ag2CrO4 we have + ¿¿ 2 ¿
A g¿
¿

KspAg2CrO4 so that the onset of silver chromate precipitation occurs where [Ag+] = √ ❑ . Solving

these two equations and solving for the chromate concentration provides [chromate]= K spAg 2CrO 4 /

KspAgCl. By equating these two results we find KspAg2CrO4 = 1.1 x 10-12 M3 and KspAgCl = 1.81 x 10-10 M2, we

2−¿
have Cr O¿4 =6mM. A lower chromate concentration may be used, because chromate itself is colored.
¿
This will lead to a possible l “overshoot” of the equivalence point somewhat before silver chromate starts

to precipitate. To correct for the formation some precipitate before it is a blank must be titrated solution,

and corresponding volume should be subtracted from titrant volume Vt. In this second experiment, the

concentration of chloride in water is determined using a weight based titration based on the Mohr method.

The end point is apparent by the formation of a orange-brownish silver chromate precipitate.

Experimental

Experiment 1

Two crucibles are brought to a constant mass by heating at 110 ℃ for an hour. Two 100-mL water samples

are mixed with about 2-3 mL of 6 M HNO3 to each sample. 0.2 M AgNO3 is added and mixed with

each solution until AgCl coagulates, followed by an additional 3 to 5 mL. Heat and digest the
 3

solids for about 10 min. Add a few drops of AgNO3 to confirm that precipitation occurred. Each

beaker is covered and stored in a dark place for a week. The following week, the solutions are

decanted through the weighed crucibles. The precipitates are washed several times with 2 to 5

mL of 6 M HNO3 per liter of deionized water, and are then decanted through the filters. Transfer

the AgCl from the beakers to the individual crucibles with fine streams of wash solution.

Continue washing until the filtrates are essentially free of Ag+ ion. The precipitate should be

dried at 110 °C for at least 1 hr. Store the crucibles in a desiccator while they cool. Weight the

mass of the crucibles and the samples. Repeat the cycle of heating, cooling, and weighing until

two consecutive weighings.. Calculate the concentration of chloride ions in the water sample.

After analysis has been completed remove the precipitates by tapping the crucibles over a piece

of paper. Transfer the collected AgCl to the waste container. Remove any traces of AgCl by

filling the crucibles with 6 M NH3 and allowing them to stand.

Experiment 2

In this second experiment three samples are prepared with 50 mL of the unknown chloride

sample, an additional 50 mL of water to bring the total volume of 100 mL, and 1 mL of indicator

(potassium chromate). Prior to this, a blank consisting of 50 mL of DI water, a small amount of

calcium carbonate, and 1 mL of indicator 5% K2CrO4 is prepared. The addition of the silver

nitrate titrant is added dropwise, until an orange-brownish color change is observe. The bottle

of silver nitrate is weighed prior to its addition and after each use for each of the three samples.

The unknown chloride samples should be prepared as previously mentioned, and then silver
 4

nitrate should be added dropwise until the color change is observed. The reagent weights should

be corrected for the blank, and the concentration of chloride in the unknown is determined using

the average of the three determinations.

Results and Calculations

For this experiment

Table 1: Weight of Crucibles

Weighing # Mass of Crucible 1 (g) Crucible 2 (g)

1 33.9870 33.8356

2 33.9846 33.8351

3 33.9903 33.8359

4 33.9901 33.8357

5 33.9906 33.8364

Average 33.9894 33.8354

Table 2: Weight of Crucibles with Sample

*Note for sample 2 that a different crucible was utilized than listed in Table 1, to account for that
the average mass of the crucible utilized was 35.8266g, and it’s weight with the sample was
35.8683
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Sample # Mass of Sample+Crucible (g) Mass of Sample (Mass of

Sample+crucible)-(Average
Mass of Crucible from Table
1) (g)

1 34.0321 .0427

2 35.8683 .0417

After determining the mass of the sample, the concentration of chloride was determined as
demonstrated in the sample calculation below:
Ex. for Sample 1

−¿
−¿=105.62mg Cl¿
g Cl−¿
35.45 =0.0105617 g Cl ¿
mol g
143.33 AgCl
mol
M Cl −¿

=0.0427 g AgCl x ¿
M AgCl
Cl−¿ =m AgCl x ¿
m¿

Concentration of chloride=105.62 ppm

Chloride concentration of Sample 2: 103.14ppm

Table 3: Average chloride concentration and Standard Deviation

Calculated Chloride
Analyst
Concentration (ppm)
102.0
101.7
107.6 Average = 105.4
105.1 s = 2.8
108.8
109.4
105.6
103.1
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¿ 110−105.4∨ ¿ x 100=4.2 error

110
¿ Expected conc .−Calculated conc .∨ ¿ x 100=¿
Expected conc .
Percent error=¿

N = 8 data points → N-1 = 7 → at 95% confidence, t = 2.365

ts
Confidence Interval : µ=x ±
√❑

Comparing the Experimental Mean to the True Value (110 ppm Cl-)

¿ µ−x∨ ¿ √❑
s
t calc=¿

Experiment 2:

The mass of silver nitrate was determined by subtracting the differences in the mass of the

dropper bottle from the difference of the mass of silver nitrate use with the blank (0.77g). The

differences in mass of silver nitrate for trials 1, 2, and 3 were a respective 3.437g, 3.253g, and

2.645g. After accounting for the blank the masses were a respective, 2.667, 3.253, and 2.645g.

The chloride concentration was then determined utilizing similar calculations to the one below:

0.4877 molAgNO 3 35.453 mg

Ex. for Sample 1: x 2.667 g x x 20=92.2 ppm
kg solution mmol

Table 4: Calculated chloride concentration (ppm), average, concentration, and the standard deviation

Calculated Chloride Average = 103.7

Analyst
Concentration (ppm) s = 6.80
106
118.3
106.1
104.2
102.9
104.7
105.0
100.7
102.5
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101.6
92.2
112.5
91.5

¿ 110−103.71∨ ¿ x 100=5.72 error

110
¿ Expected conc .−Calculated conc .∨ ¿ x 100=¿
Expected conc .
Percent error=¿

N = 13 data points → N-1 = 12 → at 95% confidence, t = 2.179

ts
Confidence Interval : µ=x ±
√❑

Comparing the Experimental Mean to the True Value of 110 ppm Cl -

¿ µ−x∨ ¿ √❑
s
t calc=¿

Comparison of Two Experimental Means

s pooled =√❑

x 1−x 2
t calc= √❑
s pooled

Comparison of Precision:

From Table 4-4 in the textbook, at df1=7, df2=12, Ftable = 2.91

2 2
s1 (2.8)
Fcalc = 2
= 2
=0.169< 2.91→ difference is significant
s2 (6.8)

The following test demonstrates that the two standard deviations are significantly different
from each other.
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Discussion and Results

In these experiments, gravimetric and argentometric methods were conducted in order to

determine the concentration of an unknown chloride solution. Several calculations were done to

account for the differences in these methods, and to evaluate which method was more efficient

for this determination. Utilizing the calculations done for the critical value 4 of the gravimetric

precipitation values fell within the 95% confidence interval, whereas only 1 of the argentometric

titration values fell within the 95% confidence interval. These results demonstrated that the

gravimetric methods were more accurate in obtaining results within their independent range.

When comparing the percent errors, the argentometric titration yielded a 5.72% error from the

actual concentration of chloride (110 ppm), while the gravimetric precipitation yielded a 4.2%

error. This further demonstrates that the gravimetric precipitation is slightly more accurate than

the argentometric titration, and has slightly fewer errors. On the other hand, both tests failed the

t-test which had compared the experimental means to the true value. This is significant as this

would show that neither method held an advantage over the either in the determination of

chloride concentration, if simply accounting for the t-test The argentometric method seemed to

have yielded several outliers within the data including the second data point with a value of

118.3 when compared to Brandon’s other values, and the value of 112.5 for the second to last

data point collected from my second trial. These results may have been due to varying errors

which will be discussed below.

Several systematic and random errors during the experimentation between the two

methods. The t-test for both results was rejected, demonstrating that neither result had an

advantage over the other. However, this may have been due to any errors during the process of

experimentation or any systematic errors that may not have been accounted for. In order to
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account for systematic errors in the gravimetric titration a better system could be employed in

drying, cooling, and weighing the crucibles. Keeping the time between each interval of drying

and cooling consistent, would provide a more efficient manner of weighing the crucibles and

would reduce potential deviations in the data. Argentometric titrations may have been affected by

overshooting the equivalence point, which had been accounted for by the preparation of a blank.

Argentometric titrations may be suspect to more random errors than gravimetric methods due to

the potential of overshooting, inconsistent pipetting of the various chemicals which would lead to

the varied concentrations, potential contaminants, and the addition of inconsistent amounts of the

silver nitrate. To account for any inconsistencies in the mixing, withdrawal, or addition of certain

chemicals an automated pipettor could have been used to account for any personal errors that

may have occurred. This would lead to consistent amounts of each chemical for each

trial/sample. Additionally, instead of simply adding the silver nitrate to the unknown chloride

mixture until the color change is noted, an added step of counting the number of drops of silver

nitrate added should be enforced to ensure that an equivalent amount is added while titrating for

each sample. Any random errors with the gravimetric errors may have included potential

contaminants within the sample, additional moisture within the crucibles, and incomplete

washing. These random errors, as demonstrated by the percent errors of each individual method,

were less significant for the gravimetric method when compared to the argentometric method.

While neither the gravimetric nor the argentometric method demonstrated to have had a

significant overall advantage in the determination of chloride, the gravimetric had a lower

percent error when compared to that of the argentometric. Overall, the gravimetric precipitation

method demonstrated a greater effectiveness for determining the concentration of chloride in an

unknown solution when compared to that of the argentometric titration method due to a lower
 10

percent error in addition to a larger amount of values that fell within the critical value test. . Both

of these methods demonstrated an ability to determine the concentration of chloride and are

practical methods for environmental testing, however, the gravimetric method simply

demonstrated a greater ability to do so.

Questions for Experiment 1

1. What would happen if you carried out the precipitation of chloride ions in a neutral
medium?

If the precipitation of chloride ions were carried out in a neutral medium the anions of the weak acids

would form precipitates with Ag+ that would interfere with precipitation of the analyte. The solution

has to be kept acidic during precipitation to eliminate interference from anions of weak acids that form

soluble salts in a neutral medium.

2. Why does the wash solution contain HNO3 and not NaNO3? Why is it not deionized water or
AgNO3 solution?

The wash solution contains HNO3 in order to keep the solution mildly acidic to maintain the

electrolyte concentration and prevent interference from soluble salts that could form. It also eliminates

the possibility of peptization during the washing step causing the acid to decompose into a volatile

product when the precipitate is dried. . DI water isn’t used because it causes peptization, and the usage

NaNO3 and AgNO3 would cause too much interference during the precipitation of the analyte.

3. How would the results of this analysis be affected if photodecomposition of silver chloride
took place before filtration, and the additional reaction (shown below) occurred?
3Cl2(aq) + 3H2O + 5Ag+ 5AgCl(s) + ClO3- + 6H+
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The photodecomposition of silver chloride would lead to the chloride being used up at a faster rate

than it’s being produced, leading to a chloride amount lower than the true value.

4. A 5.000-g sample of a pesticide was decomposed with metallic sodium in alcohol, and the
liberated chloride ion was precipitated as AgCl. Express the results of this analysis in terms
of the percentage of 1,1,1-trichloro-2,2-bis(parachlorophenyl)ethane (DDT) (C 14H9Cl5) based
upon the recovery of 0.1606 g of AgCl.

?=determine amount of DDT produced in the pesticide utilizing a recovered 0.1606g of AgCl

354.34 g DDT
5 mol Cl−¿ x =0.079 g DDT
1 mol
Cl−¿ 1 mol DDT
1 mol x
1mol AgCl ¿
1mol AgCl
0.1606 g AgCl x x¿
143.35 g

0.079 g DDT
Percentage of DDT = x 100=1.6 DDT
5 g sample

5. Addition of an excess AgNO3 to a 0.5012-g sample yielded a mixture of AgCl and AgI that
weighed 0.4715 g. The precipitate was then heated up in a stream of Cl 2 to convert the AgI to
AgCl.
2AgI(s) + Cl2(g)  2AgCl(s) + I2(g)

The precipitate was found to weigh 0.3922 g after this treatment. Calculate the percentages of
KI and NH4Cl in the sample.

x = mass of iodine, and y = mass of chloride.

x+ y=0.4715 M AgCl=143.35 ; M AgI =234.8

x=0.4715− y

M AgCl
x+ y ( )=0.3922
M AgI
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−¿
0.4715− y+ 0.611 y=0.3922 y=0.204 g → 43.3 I ¿

0.0793=0.389 y

y=0.204 g=0.204 /0.4715 g of mixture=43.3 KI

x=0.4715−0.204=0.2675 g /0.415 g of mixture → 56.8 NH 4 Cl

Questions for Experiment 2

1. Write balanced chemical equations for all the reactions involved in this experiment.

Cl- + Ag+ → AgCl(s)

CrO42- + 2Ag+ → Ag2CrO4(s)

2. Why is solid CaCO3 suspended in the indicator blank?

It imitates the presence of AgCl within the sample used for the experiment.

3. Why was NaHCO3 added to your samples prior to titration?

This chemical was added to test the pH of the solution. The solution will bubble if it isn’t basic

enough, and it needs to be buffered in between a pH of 7-10.

4. Briefly describe how you would determine carbonate ion by the Volhard method.

A carbonate ion would be determined by the Volhard method by adding a measured excess of AgNO 3

to the solution, then filter out the AgCO 3 under back-titration. A back titration using a standard

solution of KSCN would then need to be used in order to determine the concentration of carbonate.

5. Titration of a 0.485-g sample by the Mohr method required 36.8 mL of standard 0.1060 M
AgNO3 solution. Calculate the percentage of chloride in the sample.
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−¿
Cl−¿ 35.45 g
1 mol x =0.138 gCl ¿
1 mol AgNO3 1 mol
0.1060 mol
0.0368 L AgNO3 x x¿
L
−¿
0.138 g Cl− ¿ x 100=28.5 Cl
¿
0.485 g total
m Cl −¿

x 100=¿
mtotal
−¿=¿
¿
Percentage of Cl

6. Because the yellow color of CrO42- tends to obscure the first appearance of the red Ag 2CrO4,
it is common practice to hold the CrO 42- concentration to about 2.5 x 10-3 M. Calculate the
relative titration error (neglecting the volume of AgNO 3 needed to produce a detectable amount
of Ag2CrO4) in the titration of 50.0 mL of 0.0500 M NaCl with 0.1000 M AgNO3.

1L 0.05 mol NaCl 1mol AgNO3 1L

50 mL x x x x =0.025 L=25 mL titrant
1000 mL 1L 1 mol NaCl 0.1mol
+¿
Ag ¿= √❑ M
¿

[Ag+] =

0.1V (0.05)(0.05) 1.7 x 10−10

2.608 x 10−4 =[ − ]+ V ¿ 25.211 mL
0.05+V 0.05+V 2.608 x 10−4

25.211−25 mL
Percent error= x 100=0.84
25.211

7. The Fajans method is to be used in the routine analysis of solids for their chloride
content. It is desired that the volume of standard AgNO3 used in these titrations be
numerically equal to the percent Cl- when 0.2500-g samples are used. What should the
molarity of the AgNO3 solution be?
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AgNO3+Cl- ↔ AgCl(s)+NO3-

Mass of solid sample=0.2500g Cl- %=(mass Cl-/mass sample) x 100

Volume of AgNO3 =(mass Cl-/mass sample) x 100= 100 (mass of Cl-)/0.25 1)

AgNO3 mols/L=mol of AgCl in sample= mol of Cl-/volume of AgNO3

=(0.25g Cl-)/((35.45g/mol) x (0.25g/100(mass of chloride)(value from 1)

=0.25g/(35.45g.mol)(100)=7.052x 1 0−5 M

8. (a) A 0.1752-g sample of primary standard AgNO3 was dissolved in 502.3 g of deionized
water. Calculate the weight molarity of Ag+ in this solution.

1 mol
0.1752 g AgNO3 x =1.03 x 10−3 mol AgNO3
169.87 g

Mass of solution = 502.3 g + 0.1752 g = 502.48 g = 0.502 kg solution

−3
1.03 x 10 mol AgNO3
Weight molarity = =2.05 x 10−3 mols /kg
0.502 kg soln

(b) The standard solution described in part (a) was used to titrate a 25.171-g sample of a
KSCN solution. An end point was obtained after adding 23.765 g of the AgNO3 solution.
Calculate the weight molarity of the KSCN solution.

23.765 g soln
+¿ x =1.938 x 10−3 m KSCN
25.171 g sample
2.053 x 10−3 m Ag¿

(c) The solutions described in parts (a) and (b) were used to determine the BaCl2×2H2O in
a 0.7120-g sample. A 20.102-g portion of the AgNO3 was added to a solution of the sample
and the excess AgNO3 was back-titrated with 7.543 g of the KSCN solution. Calculate the
percent BaCl2×2H2O in the sample.

Ag+¿
2.053 x 10−3 mol =¿
1 kg +¿−1.462 x 10−5 mol
+¿ x ¿ 4.127 x 10−5 mol Ag¿
2.010 x 10−2 kg Ag¿

244.265 g
2 mol Ag+¿ x
1 mol BaCl2 ∙ 2 H 2 O −3
¿ 3.26 x 10 g BaCl2 ∙2 H 2 O
1mol BaCl2
¿ 2.665 x 10−5 mol x ¿
 15

−3
mass of BaCl2 ∙ 2 H 2 O 3.26 x 10 g BaCl2 ∙2 H 2 O
BaCl2 ∙ 2 H 2 O= x 100= x 100=0.457 BaCl2 ∙ 2 H 2 O
total mass of sample 0.7120 g sample