Analytical chemistry

Analytical chemistry is the area of chemistry responsible for characterizing the composition
of matter, both qualitatively (what is present) and quantitatively (how much is present).

Analytical chemistry is the study of the separation, identification, and

quantification of the chemical components of natural and artificial materials.

Analytical chemistry is also focused on improvements in experimental design,

chemometrics, and the creation of new measurement tools to provide better chemical
information.

Analytical chemistry has applications in forensics, bioanalysis, clinical analysis,

environmental analysis, and materials analysis.
qualitative analysis characterization analysis
An analysis in which we An analysis in which we evaluate a
determine the identity of the sample’s chemical or physical
constituent species in a sample. properties.

quantitative analysis
An analysis in which we determine how fundamental analysis
much of a constituent species is present An analysis whose purpose is to improve
in a sample. an analytical method’s capabilities.
Chemical Analysis : A process that provides chemical or physical
information about the constituents in the sample or the sample itself.

Qualitative analysis Quantitative analysis

gives an indication of the identity of the determines the amount of one or more of
chemical species in the sample. these components

what is present? how much is present?

 Analytical methods can be separated into
classical and instrumental
Classical methods (also known as Instrumental methods
wet chemistry methods)
use only chemicals for separations such as use an apparatus to measure physical
precipitation, extraction and qualitative quantities of the analyte such as light
analysis by color, odor, or melting point. absorption, fluorescence, or conductivity.
Quantitative analysis is achieved by
measurement of weight or volume.
Spectroscopy

Gravimetric analysis
Electrochemistry

Volumetric analysis
Chromatography

(Chemical tests )
 a sample is a limited quantity of something
which is intended to be similar to and
represent a larger amount of that thing(s).

 The components of interest in the sample are

called analytes, Constituent : A component of a
sample; it may be further
 the remainder of the sample is the matrix. classified as:

 Technique is a chemical or physical A major constituent

principle that can be used to analyze a % 1-100
sample.

 A method is the application of a technique Minor constituent

for the determination of a specific analyte in % 0,01-1
a specific matrix.
Trace constituent
 A procedure is a set of written directions ˂ %0,01
detailing how to apply a method to a
particular sample.
 Statistical Analysis of the Results

• Measurement : An experimental
determination of an analyte’s
chemical or physical properties.

• Length :
• Mass :
• Measurement data give only an
• Time:
estimate of the ‘true’ value. • Temperature:
True Result The 'correct' value for a measurement which remains unknown except when
a standard sample is being analysed. It can be estimated from the results
with varying degrees of precision depending on the experimental method.

Mean The mean, X, is the numerical average obtained by dividing the sum of the
individual measurements by the number of measurements. (The average value
of a set of data -X-).

Median The median, Xmed, is the middle value when data are ordered from the
smallest to the largest value. Or the value for a set of ordered data, for which
half of the data is larger in value and half is smaller in value ( –Xmed).

Range (Spread ) The range, w, is the difference between the largest and smallest values in the
data set. It is a measure of precision.
Range = w = Xlargest – Xsmallest

N
∑ xi
i=1 X1 + X2 +X3 +......+ Xn
X = ------------- = ----------------------------------------
N N
Mean
Precision is the closeness of data to other data that have been obtained in exactly the same
way. Sometimes called the variability, it can be represented statistically by the
standard deviation or relative standard deviation.
Accuracy The closeness of an experimental measurement or result to the true or
accepted value. Accuracy is usually expressed in terms of error or absolute
error. (Bias)
Error The difference between the true result and the measured value.. E = xi - xt

Absolute Error defined as the actual difference between the true result and the
experimental value in the same units.
Relative Error is the absolute error divided by the true value.

Uncertainty The range of possible values for a measurement.

xi - xt
xi - x t
Er = ------------- . ‰1000
Er = ----------- . %100 Xt
Xt
(percentage relative error) (parts per thousond)
Calculate the mean, median,
absolute and relative error for the
following data set

Fe concentration

19,4ppm
19,5ppm
19,6ppm
19,8ppm
20,1ppm
20,3ppm
 Classification of Errors
On the basis of their origin, errors may usually be classified as determinate or
indeterminate.
Systematic Are the errors which can be avoided or whose mahnitude can be determined.
They are (in principle at least) measurable and for which a correction may be
(determinate) made.
Error
- operational and personal error
- instrumental and reagent error
- errors of methods
- Sampling Errors

Random They are due to causes over which the analyst has no control and which in
general are so intangible taht they are incapable of analysis. They do not
(indeterminate) have a definite measurable value.
Error

Gross Error
Statical Evulation of the Random (indeterminate) Error

2 2
– (x-μ) /2 σ
e
y= --------------------------------------

σ (2 П)^ 1/2

x herbir ölçümün değeri

μ bir çok ölçümün aritmetik ortalaması
x – μ ortalamadan sapma
σ standart sapma
y her bir x - μ değeri için bulunma frekansı
Deviation

Standard Deviation is a measure of the precision of a population of data

Variance (σ2 or s2) The square of the standard deviation. The variance is a
parameter describing in part either the actual probability distribution of an
observed population of numbers, or the theoretical probability distribution of
a sample of numbers.

Relative Standard
Deviation (RSD)
coefficient of is the percent relative standard deviation
variation
Degree of Freedom An independent variable. For N measurements it is equal to N -1
Calculate the standard
deviation of the following
experimental results
Lead concentration in blood

0,752ppm
0,756ppm
0,752ppm
0,751ppm
0,760ppm
 ∑ (xi – x1 )2 + ∑ (xi – x2 )2 + ...
Spool = ( --------------------------------------------)^1/2

N1 + N2 + N3 ... – Nt
• Calculate the stardard deviation of the method.

Sample No Number of measurements Hg concentration ppm

1 3 1,80 1,58 1,64

2 4 0,96 0,98 1,02 1,10
3 2 3,13 3,35
4 6 2,06 1,93 2,12 2,16 1,89 1,95

5 4 0,57 0,58 0,64 0,49

6 5 2,35 2,44 2,70 2,48 2,44
7 4 1,11 1,15 1,22 1,04
What are the standard deviation, the relative standard deviation, and the
percent relative standard deviation for the folowing data

3.056 - 3.080 - 3.094 - 3.107- 3.112 - 3.174- 3.198

What are the standard deviation, the relative standard deviation, and the
percent relative standard deviation for the following data

3.056 - 3.080 - 3.094 - 3.107- 3.112 - 3.174- 3.198

1,76 (±0,03) + 1,89 (±0,02 ) - 0,59(±0,02) = ?

[ 1,76 (±0,03) x 1,89 (±0,02 ) ] / 0,59(±0,02) =?

The pH of a solution is defined as
pH = –log[H+]

where [H+] is the molar concentration of H+. If the pH

of a solution is 3.72 with an absolute uncertainty of
±0.03, what is the [H+] and its absolute uncertainty?
The pH of a solution is defined as
pH = –log[H+]

where [H+] is the molar concentration of H+.

If the pH of a solution is 3.72 with an absolute
uncertainty of ±0.03, what is the [H+] and its
absolute uncertainty?
The Nature and Origin of
Errors
On the basis of their origin, errors may
usually be classified as determinate or
indeterminate. The first are those
having a value which is (in principle at
least) measurable and for which a
correction may be made. The second
fluctuate in a random manner and do
not have a definite measurable value.

Indeterminate errors arise from the

unpredictable minor inaccuracies of
the individual manipulations in a where μ is the mean and s is the standard deviation. The
procedure. A degree of uncertainty is width of the curve is determined by s, which is a useful
introduced into the result which can measure of the spread or precision of a set of results, and is
be assessed only by statistical tests. unique for that set of data. An interval of μ ± s will contain
The deviations of a number of 68.3% of the statistical sample, whilst the intervals μ ± 2s
measurements from the mean of the and μ ± 3s will contain 95.5% and 99.7% respectively.
measurements should show a
symmetrical or Gaussian distribution
Confidence Intervals for Populations
confidence interval:
Range of results around a mean value that could be
explained by random error.

there is a 68.26% probability that a member selected

at random from a normally distributed population will
have a value in the interval of
± 1.

In general, we can write

Xi = ± z

where the factor z accounts for the desired level of

confidence. Values reported in this fashion are called
confidence intervals.
Confidence intervals also can be reported using the mean for a sample of size n, drawn from a population of known . The standard
deviation for the mean value,  , which also is known as the standard error of the mean
What is the 95% confidence interval for the analgesic tablets if an analysis of five
tablets yields a mean of 245 mg of aspirin? the population standard deviation for the
amount of aspirin in a batch of analgesic tablets is known to be 7 mg of aspirin.
What is the 95% confidence interval for the analgesic tablets if an analysis of five
tablets yields a mean of 245 mg of aspirin? the population standard deviation for the
amount of aspirin in a batch of analgesic tablets is known to be 7 mg of aspirin.
 Confidence Intervals for Samples
Once the reliability of a replicate set of measurements has
been established the mean of the set may be computed as
a measure of the true mean. Unless an infinite number of
measurements is made this true mean will always remain
unknown. However, the t-factor may be used to calculate
a confidence interval about the experimental mean,

the confidence interval as a way to report the most

probable value for a population’s mean, , when the
population’s standard deviation, , is known.

Since s2 is an unbiased estimator of 2, the term z in

The confidence interval equation is replaced with the
variable t, where t is defined such that t z at all
confidence levels.

t is a statistical factor derived from the normal error curve

s is the estimated standard deviation and N is the number of
results.
t is a statistical factor derived from the normal error curve
s is the estimated standard deviation and n is the number of
results.
What is the 95% confidence interval for the folowing data?

3.056 - 3.080 - 3.094 - 3.107- 3.112 - 3.174- 3.198

The accepted value for the chloride content of
a standard sample obtained from extensive
previous analysis is 54.20%.

Five analyses of the same sample are carried

out by a new instrumental procedure,
54.01, 54.24, 54.05, 54.27, 54.11%

being the results obtained. For the 95%

confidence interval, is the new method giving
results consistent with the accepted value?
The accepted value for the chloride content of
a standard sample obtained from extensive
previous analysis is 54.20%.

Five analyses of the same sample are carried

out by a new instrumental procedure,
54.01, 54.24, 54.05, 54.27, 54.11%

being the results obtained. For the 95%

confidence interval, is the new method giving
results consistent with the accepted value?
Dixon’s Q-test. Statistical test for deciding if an outlier can be removed from
a set of data. The Q-test compares the difference between the suspected outlier and its
nearest numerical neighbor to the range of the entire data set.

outlier: Data point whose value is much larger or smaller than the remaining data.

differences between outlier and Nearest value to it

Qexp =
-------------------------------------------------------------------------
Range (spread)

Qexp is greater than Q(, n), then the null hypothesis is rejected and the outlier
may be rejected. When Qexp is
less than or equal to Q(, n) the suspected outlier must be retained.

Q (% 90 confidence 0,94 0,76 0,64 0,56 0,51 0,47 0,44 0,41

interval)
Number of measurements 3 4 5 6 7 8 9 10
The following masses, in grams, were recorded in an experiment to determine the average mass of a U.S.
penny.

3.067 3.049 3.039 2.514 3.048 3.079 3.094 3.109 3.102

Determine if the value of 2.514 g is an outlier at % 90 confidence level.

Comparing Two Sample Means
Tables below show results for two separate experiments to determine the mass of a circulating U.S.
penny. Determine whether there is a difference in the means of these analyses at a %95 confidence
level.
Tables below show results for two separate experiments to determine the mass of a circulating U.S.
penny. Determine whether there is a difference in the means of these analyses at a %95 confidence
level.
The %w/w Na2CO3 in soda ash can be determined by an acid–base titration.
The results obtained by two analysts are shown here. Determine whether the
difference in their mean values is significant at a %95 confidence level
 Comparing Two Sample Variances

F-test Statistical test for comparing two variances to see if their difference
is too large to be explained by indeterminate error. The F-test can be
extended to the comparison of variances for two samples

If Fexp is greater than Fcri, the analysis is not under statistical control.
• Tables below show results for two separate experiments to determine the mass of a circulating
U.S. penny. Determine whether there is a difference in the precisions of these analyses at %95 confidence
level. the variances are s2A = 0.00259 and s2B= 0.00138.
A new method for Ni analysis in the stainless stel is being compared with
another method, is the new method is acceptable?
the results of the analysis of vitamin B are shown below,.
81,10 79,30 80,40 79,70
Calculate confidence interval for 95% confindence level

If the true value 80,00, is there any significant difference between mean values
at a %95 confidence level
 Sistematik Belirli Hata

1- Sabit hatalar : analiz edilen numune miktarından bağımsızdır.

2- Orantılı hatalar : numunenin miktarı ile orantılı olarak azalır veya artar
 F Testi (standart sapmaların karşılaştırılması)

• İki farklı kişinin yaptığı analizlerin veya iki farklı metotla elde edilen sonuçların standart
sapmalarının karşılaştırılmasında kullanılır. Farklı sonuçların standart sapmalarının karesi birbirine
bölünür ve sonuç tablodaki F değeri ile karşılaştırılır.
 Aqueous Solution Chemistry

 Precipitation Reactions

 Acids, Bases, and Neutralization Reactions

 Oxidation–Reduction (Redox) Reactions

 Complex formation reactions

 Solutions
Homogeneous mixtures are called solutions.

Solvent solute
is the component present in greatest is a component present in a lesser
amount or determines the state of quantity and it is said to be dissolved
solution exist in the solvent.
Solvent is the component present in A solute is a component present in a
greatest amount or determines the state of lesser quantity and it is said to be
solution exist.
dissolved in the solvent.
Solubility is the maximum amount of solute that dissolves in a given
quantity of solvent at a specific temperature to produce a
saturated solution

saturated The solution in which no more solute can be dissolved is

solution. said to be saturated solution.

Super saturated is a solution in which has higher amount of solute than

solution. saturated solution

Unsaturated is a solution in which contain less amount of solute than

solution saturated solution
nonelectrolyte Substances such as sucrose or ethyl alcohol, which do not produce ions in
aqueous solution, are called nonelectrolytes.

electrolytes Substances such as NaCl or KBr, which dissolve in water to produce

conducting solutions of ions, are called electrolytes.

strong electrolytes, weak electrolytes.

Compounds that dissociate to a large extent compounds that dissociate
(~100%) into ions when dissolved in water are to only a small extent are weak electrolytes.
said to be strong electrolytes,
 Solution Concentrations

Mass of solute
Percent by mass = ------------------------ x 100
Mass of solution

Volume of solute
Percent by volume = ------------------------- x 100
Volume of solution

Mass of solute
Mass / volume percent = --------------------- x 100 (gr/100ml)
Volume of solution
 Solution Concentrations

Number of moles of solute

Molarity = -----------------------------------------------
Number of liters of solution

Number of moles of solute

Molality = --------------------------------------------------
Number of kilograms of solvent

Moles of component i
Mole fraction = ---------------------------------------------------------
total moles of all solution components

Parts per million (ppm), Parts Per Billion(ppb)

mg solute g solute
1 ppm = -------------------- 1 ppb = -----------------------
kg solution kg solution
Mol m
number n = ---------
MA
Molarity n
M= ------- mol/L
V
density m
d = ---------- gr/mL
V
 Diluting Concentrated Solutions

Minitial x Vinitial = mol number = Mfinal x Vfinal

Minitial x Vinitial = Mfinal x Vfinal

Dilution The addition of solvent to solution is called dilution. it does not change the
amount of solute in a solution but changes the solution concentration..
Find the molarity of a solution that 23.4g of Na2SO4 was dissolved in water and diluted to
250.0ml Na2SO4: 142
calculate the molarity of H2SO4 solution when we dilute 50.0 mL of a
solution of 2.00 M H2SO4 to a volume of 200.0 mL.
There is a 2000ml of 8M H2SO4 solution in the lab. A student needs 800ml of 2M
H2SO4 solution to carry out an experiment. In order to prepare this solution a-
how many ml of 8 M H2SO4 solution should the student use? b- how many ml of
distilled water should be added?

Calulate the molarity of the solution prepared by mixing 400ml of 0.6M HNO 3
solution with 200ml water?
Q1 How can you prepare 500ml 0.10 M H2SO4 solution from 3.0M H2SO4?

Q2 How would you prepare 500.0 mL of 0.2500 M NaOH solution starting from a
concentration of 1.000 M?
Q3 What is the final concentration if 75.0 mL of a 3.50 M glucose solution is diluted
to a volume of 400.0 mL?
• question.
A solution has a density of 1.235g/ml and contains 90.0%
glycerol C3H8O3 and 10% H2O by mass. Determine

a- the molarity of C3H8O3

b- the molarity of H2O
c- mole fraction of C3H8O3
d- mole percent of H2O
e- the molality of H2O
 Reactions in Aqueous Solution

Precipitation Are the reactions, an insoluble solid is formed, the solid

reactions product is called as a precipitate.

Ag+(aq) + Cl-(aq) → AgCl(s)

Solubility is the maximum amount of solute that dissolves in a given
quantity of solvent at a specific temperature to produce a
saturated solution

saturated The solution in which no more solute can be dissolved is

solution. said to be saturated solution.

Super saturated is a solution in which has higher amount of solute than

solution. saturated solution

Unsaturated is a solution in which contain less amount of solute than

solution saturated solution
• Solubility of most of solids increase with temperature.

• Solubility of gases decrease with increased temperature

• Solubility of a gas increases as the gas pressure is increased.

• Types of solvent and solute is important,

like dissolves like, generally nonpolar substances are soluble in nonpolar
substances, polar solvents dissolves ionic and polar substances.
solubility rules
Soluble salts

salts of 1A groups (Na, K, Li,) and NH4+ are soluble

all nitrates, acetates and perchlorates are soluble

NO3 (Nitrat), CHCOO- (asetat) ,ClO4 (perklorat)

all chlorides (halogens) are soluble except (AgCl, Hg2Cl2, PbCl2)

most sulfates (SO42+ ) are soluble except (Sr SO4, Ca SO4 , Ba SO4 , Pb SO4 )

Cl-, Br-, I- SO42-

Li+, Na+, K+, Rb+, Cs+ NH4+ NO3- ClO4- CH3CO2-
solubility rules

Slightly soluble

all OH- hydroxides are insoluble except those of 1A group (Na, K, Li,) and NH4+

all sulfides S2- are insoluble except those of 1A group (Na, K, Li,) and NH4+

all carbonates are insoluble except those of 1A group (Na, K, Li,) and NH4+

All PO43- are insoluble except those of 1A group (Na, K, Li,) and NH4+

CO32-, PO43- OH-, S2-

• What will happen if Na2CO3 and CaCl2 solutions are mixed ?

• What will happen if CuSO4 and NaNO3 solutions are mixed ?

 Ionic compounds of alkali metals (like NaCl, KBr,
solubility product LiNO3 ..) generally dissolve completely in water.
constant But many ionic compounds are only slightly
soluble in water. We use the term insoluble for such
compound.
SrCrO4(s)  SrCrO4(aq)
Ksp is the solubility product constant and is equal
SrCrO4(aq)  Sr2+(aq) + CrO42-(aq)
to the product of the concentration of the ions

Ksp = [Sr2+] [CrO42-] involved in the equilibrium, each raised to the

power of its coefficient in the equilibrium equation.
Ksp has a fixed value for a given system at a
particular temperature.

Solubility equilibrium Ksp Solubility equilibrium Ksp

1.6x10-24
Al(OH)3  Al3+ + OH- 1.3x10-33 ZnS  Zn2+ +S2-
5.1x10-9 3.5x10-8
BaCO3 Ba +CO3
2+ 2-
MgCO3 Mg +CO32+ 2-

1.6x10-5 1.8x10-10
PbCl2  Pb + 2Cl
2+ - AgCl  Ag + Cl
+ -
question: write the solubility product constants
for

Ca3(PO4)2, Ag2CrO4, CaF2, PbSO4

 question: solid barium sulfate is shaken in
Solubility and Ksp
contact with pure water at 25°C for several days.
At the equilibrium saturated barium sulfate

Solubility is the quantity of solution contains 1.04x10-5M Ba2+, what is the Ksp
substance that dissolves in a given for BaSO4
quantity of water. It is often
expressed as grams of solid per
100g of water. Ksp and solubility are
related and one can be calculated question: Ksp for CaF2 is 3.9x10-11, what is the
from other. solubility of CaF2 in water in grams per liter.
Common ion effect

The solubility of a slightly soluble ionic

compound is lowered when a second
soluble that furnishes a common ion is
added to solution.

question: calculate the molar solubility of

Ag2SO4 in 1.0 M Na2SO4. Ksp for Ag2SO4 is
1.4x10-5
 Ksp and Precipitate
Qip is generally called ion product, it is the
formation
product of ion concentrations raised to
appropriate powers.
Qip < Ksp no precipitate occur

SrCrO4(aq)  Sr2+(aq) + CrO42-(aq)

Qip = Ksp solution just saturated

Qip = [Sr2+] [CrO42-]

Qip > Ksp precipitation should occur
 Selective prepicitation or fractional precipitation

One ion is precipitated while the other(s) remains in solution. For this purpose there
must be significant differences in their Ksp.

question: 0.10 M AgNO3 is adding slowly to a solution that has [CrO42-] = 0.010M

and [Br-]= 0.10M ( Ksp for Ag2CrO4 is 1.4x10-5, Ksp for AgBr is 5.0 x10-
13
)

show that AgBr (s) precipitates before than Ag2CrO4(s)

at the point where Ag2CrO4 begins to precipitate, what is the [Br-] remaining in
solution?
is separation of Br- and CrO42- by fractional precipitation feasible?
Activity Effects

activity
True thermodynamic constants use a species activity in place of its molar concentration (a).

activity coefficient
The number that when multiplied by a species’ concentration gives that species’ activity ().

ionic strength
A quantitative method for reporting the ionic composition of a solution that takes into account the greater
effect of more highly charged ions ().
Calculate the ionic strength of 0.10 M NaCl.
Repeat the calculation for a solution of 0.10 M Na2SO4.
Calculate the solubility of Pb(IO ) in a matrix of
3 2

0.020 M Mg(NO ) .3 2
 Quantitatif Analysis

Titrimetry and Gravimetry

Gravimetry: is a method in which the signal is

a mass or change in mass to find the amount
(or concentration) of analyte in the sample. .
 2 H2 (g) + O2 (g)  2 H2O (s)

2 molecules of H2 1molecules O2

two moles of H2 reacts with one mole O2 and two moles H2O is produced.

4 grams of H2 reacts with 32 g O2 and 36 g H2O is produced.

 Reaksiyon Stokiometrisi

2 H2 (g) + O2 (g)  2 H2O (s)

2 molekül H2 1 molekül O2 ile reaksiyona girer 2 molekül H2O oluşur

2 mol H2 1 mol O2 ile reaksiyona girer ve 2 mol H 2O oluşur

4 gram H2 32 g O2 ile reaksiyona girer ve 36 g H 2O oluşur

what mass of AgBr is formed when a solution containing 3.45 g of KBr
is mixed with a solution containing 7.28 g AgNO3?

KBr(aq) + AgNO3 (aq)  AgBr(s) + K+ (aq) + NO3- (aq)

 Gravimetry: is a method in which the signal is a mass or change in mass to find the
amount (or concentration) of analyte in the sample.
Types of Gravimetric Methods

precipitation A gravimetric method in which the signal is the mass of a precipitate.

gravimetry Fe3+ + OH- → Fe(OH)3 →Fe2O3

volatilization A gravimetric method in which the loss of a volatile species gives rise to the
signal. In determining the moisture content of food, thermal energy vaporizes the H2O. The
gravimetry amount of carbon in an organic compound may be determined by using the chemical energy of
combustion to convert C to CO2.
CaCO3 (k)→CaO (k) + CO2(g)

electrogravimetry A gravimetric method in which the signal is the mass of an electrodeposit on

the cathode or anode in an electrochemical cell.

particulate the analyte is determined following its removal from the sample matrix by
filtration or extraction. The determination of suspended solids is one
gravimetry example of particulate gravimetry.
 Quantitative Calculations In precipitation gravimetry
the relationship between the analyte and the precipitate is determined by the
stoichiometry of the relevant reactions.
Fe3+ + OH- → Fe(OH)3 →Fe2O3

Grams of analyte = k grams of precipitate

Gravimetric factor : is a stochiometric ratio between the analyte and its precipitate

2 Formula weight of Fe
GF = ---- x --------------------------------------
1 molecular weight of Fe2O3

2x 56
Mass of the Fe = the mass of the precipitate x --------------------------
160
 Quantitative Calculations In precipitation gravimetry
the relationship between the analyte and the precipitate is determined by the
stoichiometry of the relevant reactions.

mass of the analyte X

% X (the percentage of analyte) = --------------------------------------- x 100
sample mass
Grams of analyte = k grams of precipitate

Gravimetric factor : is a stochiometric ratio between the analyte and its precipitate

a Formula weight of the analyte

GF = ---- x ----------------------------------------------------
b molecular weight of the final precipitate

Mass of X analyte = the mass of the precipitate x GF

An ore containing magnetite, Fe3O4, was analyzed by dissolving a 1.5419 –g sample in
concentrated HCl, giving a mixture of Fe 2+ and Fe3+ . After adding HNO3 to oxidize any
Fe2+ to Fe3+ the resulting solution was diluted with water and the Fe3+ precipitated as
Fe(OH)3 by adding NH3. After filtering and rinsing, the residue was ignited, giving
0.8525 g of pure Fe2O3. Calculate the
%w/w Fe3O4, in the sample.
An impure sample of Na3PO3 weighing 0.1392 g was dissolved in 25 mL of water. A
solution containing 50 mL of 3% w/v mercury(II) chloride, 20 mL of 10% w/v sodium
acetate and 5 mL of glacial acetic acid was then prepared. The solution containing the
phosphite was added dropwise to the second solution, oxidizing PO3 3– to PO4 3– and
precipitating Hg2Cl2. After digesting, filtering, and rinsing, the precipitated Hg2Cl2 was
found to weigh 0.4320 g. Report the purity of the original sample as %w/w Na3PO3

Phosphorus has an oxidation state of +3 in PO3 3– and +5 in PO4 3–; thus,

oxidizing PO3 3– to PO4 3– requires two electrons.

The formation of Hg2Cl2 by reduction of HgCl2 requires 2 electrons as the oxidation

state of each mercury changes from +2 to +1.

Since the oxidation of PO3 3– and the formation of Hg2Cl2 both require two electrons,
we have Moles Na3PO3 = moles Hg2Cl2
An impure sample of Na3PO3 weighing 0.1392 g was dissolved in 25 mL of water. A solution
containing 50 mL of 3% w/v mercury(II) chloride, 20 mL of 10% w/v sodium acetate and 5 mL of
glacial acetic acid was then prepared. The solution containing the phosphite was added dropwise
to the second solution, oxidizing PO3 3– to PO4 3– and precipitating Hg2Cl2. After digesting,
filtering, and rinsing, the precipitated Hg2Cl2 was found to weigh 0.4320 g. Report the purity of the
original sample as %w/w Na3PO3

Moles Na3PO3 = moles Hg2Cl2

Soru: to find the %w/w of NaCl in a mixture, 0,9532 g sample is disolved in
pure water and precipitated with AgNO3. After drying the AgCl precipitate ie
weighed 0,7033g. What is the %w/w of NaCl in a mixture? (NaCl: 58,44
AgCl: 143,32)
A typical gravimetric analysis procedure may be divided into five stages:
sample pretreatment; precipitation; filtration; drying and ignition; weighing.

1- sample pretreatment

2 - precipitation;

3- filtration;

5- drying and ignition;

6- weighing.
 Çökelek ve çöktürücülerin özellikleri.
Precipitant A reagent that causes the precipitation of a soluble species. Must
be selevtive for one analyte.

Precipitate: is the product of a simple reaction between the analyte and

precipitant. The precipitate must be formed quantitatively and within a
reasonable time. Its solubility should be low enough for a quantitative
separation to be made. It must be readily filterable and, if possible, have a
known and stable stoichiometric composition when dried so that its weight can
be related to the amount of analyte present. Failing this, it must be possible to
convert the precipitate to a stoichiometric weighable form (usually by ignition).
The theoretical and experimental details of precipitation gravimetry
Precipitates form in two ways; by nucleation and by particle growth.

Nucleation : A few ions, atoms or molecules come together to

form a stable solid.

Particle growth is the addition of new preciptates onto existing

nucleus..

If nucleation predominates, a large number of very small particles results, if

particle growth predominates a smaller number of larger particles is obtained.
Solutions with a large, positive value of When RSS is small, precipitation is more
relative supersaturation (RSS) show likely to occur by particle growth than by
high rates of nucleation, producing a nucleation.( smaller number of larger
precipitate consisting of numerous small particles is obtained)
particles.
Controlling Particle Size
Following precipitation and digestion, the precipitate must be separated from the supernatant solution and freed of
any remaining impurities, including residual solvent. These tasks are accomplished by filtering, rinsing,and drying
the precipitate. The size of the precipitate’s particles determines the ease
and success of filtration. Smaller, colloidal particles are difficult to filter because they may readily pass through
the pores of the filtering device. Large, crystalline particles, however, are easily filtered.
A solute’s relative supersaturation, RSS, can be expressed as

Q is the solute’s actual concentration,

S is the solute’s expected concentration at equilibrium,
Q – S is a measure of the solute’s supersaturation when precipitation begins.3
A large, positive value of RSS indicates that a solution is highly supersaturated. Such
solutions are unstable and show high rates of nucleation, producing a precipitate
consisting of numerous small particles. When RSS is small, precipitation is more likely
to occur by particle growth than by
nucleation.
Colloidal solution: the particle size are in the range of 10 -7-10-4 cm. colloidal solutions
are genereally not filterable.
Crystalline suspensions. Particle size are around 10-1 mm, they have the tendency to
precipitate.

A precipitate’s solubility usually increases at higher temperatures, and adjusting pH

may affect a precipitate’s solubility if it contains an acidic or basic anion.

Temperature and pH, therefore, are useful ways to increase the value of S. Conducting
the precipitation in a dilute solution of analyte, or adding the precipitant slowly and
with vigorous stirring are ways to decrease the value of Q.

When RSS is higher, colloidal solutions will form, when RSS is lower crystalline
solutions will form
Colloidal solution:
coagulation The process of smaller particles of precipitate clumping together to
form larger particles.
Heating and string.

Peptization İs a process by which a coagulated colloid returns to smaller particles.

It could be happen when preciptate is being washed. HNO3, HCl,
NH4Cl gibi elektrolitler eklenir.
A 101.3-mg sample of an organic compound known to contain Cl is burned in pure O2 and the
combustion gases collected in absorbent tubes. The tube used to trap CO2 increases in mass by
167.6 mg, and the tube for trapping H 2O shows a 13.7-mg increase. A second sample of 121.8 mg
is treated with concentrated HNO3 producing Cl2, which subsequently reacts with Ag +, forming
262.7 mg of AgCl. Determine the compound’s composition, as well as its empirical formula.
 Çökeltinin Saflığı

Normal olarak çözeltide kalması istenen bileşiklerin çökeltiye geçmesi safsızlıklara,

ürün kütlesinin yanlış tartılmasına dolayısıyla analizde hataya neden olur.

Yüzey Adsorpsiyonu normal koşullarda çözünen bileşiğin çöken teneciklerin

yüzeyinde tutunmasıdır. Koloidal çökeleklerde görülür. Yıkama,
Yeniden çötürme ile azaltılabilir.
Karışık kristal kristalin yapısında bulunan bir iyonun yerine ortamda bulunan
oluşumu başka bir iyonun yer değiştirerek çökmesidir.
Hapsetme ve kristaller arasındaki boşluklarda bir bileşiğin kalmasıdır. Yavaş
Mekanik çötürme ve bağıl aşırı doygunluk kontrol edilerek azaltılır.
sürüklenme
 Titration

• Titration is a procedure for determining the concentration of a solution

by allowing a carefully measured volume to react with a standard solution
of another substance, whose concentration is known. By finding the volume
of the standard solution that reacts with the measured volume of the first
solution, the concentration of the first solution can be calculated.

• equivalent point
The point that all reactants are consumed, Stoichiometric mol numbers of both
reactants are equal.

• an indicator a compound that change its color around equivalent point. such
as phenolphthalein, is colorless in acidic solution but turns pink in basic
solution.
Calculations in the volumetric titrimetry

Mol number m
n = ---------
MA
Molarity n
M= ------- mol/L
V
 Calculations in the volumetric titrimetry

aA + bB ↔ cC + dD

a mol A react with b mol B

When A is a standard (titrant) the volume of A used in the titration and its molarity
can be used to calculate the mol number of B
A 25.0 mL sample of vinegar (dilute acetic acid, ) is titrated and
found to react with 94.7 mL of 0.200 M NaOH. What is the molarity
of the acetic acid solution?
Soru: antiasit ilaç tabletlerinin anabileşeni CaCO3 tür. 0.542 gr olarak tartılan bir
tablet HCl ile titre edildiğinde, reaksiyonun tamamlanması için 38.5 ml 0.200M
HCl harcandığına göre tablet içindeki CaCO3 yüzdesi nedir?

CaCO3 + HCl → Ca2+ + CO2 + Cl- + H2O

soru: 0,2879g sodyum okzalatı (Na2C2O4) asidik çözeltide aşağıdaki redoks
tepkimesine göre titre etmek için 25,12mL KMnO 4 çözeltisi harcandığına göre
KMnO4 ün molaritesi nedir?

C2O42- + MnO4- → Mn2+ + CO2

Titrimetric Analysis
konsantrasyonu bilinen bir çözeltinin analit ile reaksiyona giren miktarının ölçümüne
dayanan kantitatif analiz metotlarıdır. Standart çözelti reaksiyon tamamlanıncaya dek
ortama yavaş yavaş eklenir.

Volumetry Gravimetric Titrimetry Coulometric titrimetri

Standart reaktifin Standart reaktifin kütlesinin Analit ile bir reaksiyonun

hacminin ölçülmesi ölçülmesine dayanan titrimetrik tamamlanması için gerekli
temeline dayanan bir metottur kulon cinsinden yük
titrimetrik metottur miktarının ölçüldüğü
titrimetrik metottur.
- İndirgenme-Yükseltgenme
reaksiyonları
- Asit Baz reaksiyonları
- Kompleks oluşum
reaksiyonları
- Çöktürme titrasyonları
Titrant: The reagent added to a solution containing the analyte and whose volume is the
signal.

titration: is a process in which a standard reagent is added to a solution of an analyte until the
reaction between the analyte and reagent is completed.

equivalence point The point in a titration where stoichiometrically equivalent amounts of

analyte and titrant react.

Indicator A colored compound whose change in color signals the end point of a titration.

end point The point in a titration where we stop adding titrant.

titration error The determinate error in a titration due to the difference between the end
point and the equivalence point.

Veq:

Venepoint:
Acids and Bases
 Acids and Bases
Acids;
Bases
Have a sour taste,
Have a bitter taste,
dissolve metals such as zinc Have a slippery feel
and carbonate minerals change color of litmus to blue,
change color of litmus to red React with dissolved metal to
form prepiciate
Acetic acid in vinegar,
Household cleaning products
Citric acid in lemons
 Acid-Base Definitions

Arrhenius Acid-Base Brønsted-Lowry Acid-Base Lewis acid-base

Definition Definition Definition
 Arrhenius Acid-Base Definition (1884)

An acid is a substance that contains hydrogen and dissociates to

produce Hydrogen ion : H+

HCl(aq)  H+(aq) + Cl-(aq)

A base is a substance that contains the hydroxyl group and

dissociates to produce Hydroxide ion : OH –

NaOH (aq)  Na+ (aq) + OH -(aq)

Neutralization is the reaction of an H+ ion from the acid and

the OH - ion from the base to form water, H2O

H+(aq) + OH-(aq) <=> H2O(l)

 Brønsted-Lowry Acid-Base Definition (1923)
An acid is a species having a tendency to donate an H+ ion.

HCl + H 2O  Cl– + H 3O+

A base is a species having tendency to accept an H+ ion.

NH3 + H 2O  NH4+ + OH-

The Conjugate Pairs in Some Acid-Base Reactions

Conjugate Pair

Acid + Base Base + Acid

Conjugate Pair
In the Brønsted-Lowry perspective, one species donates a proton and another
species accepts it: an acid-base reaction is a proton transfer process.

question : show the conjugated acid base pairs in the reactions

below
HF + H2O  F– + H3O+

H2PO4– + OH–  HPO42– + H2 O

NH4+ + CO32–  NH3 + HCO3–

 The Lewis acid-base definition :

• A base is any species that donates an electron pair

• An acid is any species that accepts an electron pair.
 Strengths of Acids

• Strong Acids; An acid that completely ionized in water, is

called as a strong acid

• HCl(aq) + H2O  H3O+(aq) + Cl-(aq)

• Weak acid is an acid that partly ionized in water.

• CH3COOH (aq) + H2O CH3COO-(aq) + H3O+(aq)

 Percent Ionization
HA + H2O ↔ H3O+ + A-

[H3O+] from HA
Degree of ionization =
[HA] originally

[H3O+] from HA
Percent ionization = x 100%
[HA] originally
Strong acids.
1. The hydrohalic acids HCl, HBr, and HI
2. Oxoacids in which the number of O atoms exceeds the number of ionizable H
atoms by two or more, such as HNO3, H2SO4, HClO4

Weak acids.
1. The hydrohalic acid HF
2. Those acids in which H is bounded to O or to halogen, such as HCN and H2S

3. Oxoacids in which the number of O atoms equals or exceeds by one the number
of ionizable H atoms, such as HClO, HNO2, and H3PO4
4. Organic acids (general formula RCOOH), such as CH3COOH and C6H5COOH
Strong bases. A base that completely ionized in water, is called as a strong base.
Soluble compounds containing O2- or OH- ions are strong bases.

NaOH (aq)  Na+ (aq) + OH -(aq)

1) M2O or MOH, where M= Group 1A(1) metals (Li, Na, K, Rb, Cs)
2) MO or M(OH)2, where M = Group 2A(2) metals (Ca, Sr, Ba) [MgO and Mg(OH)2
are only slightly soluble, but the soluble portion dissociates completely.]

A weak base is a base that partly ionized in water. Many compounds with an
electron-rich nitrogen are weak bases (none are Arrhenius bases). The common
structural feature is an N atom that has a lone electron pair in its Lewis structure

NH3(g) +H20(l)  NH4+ (aq) + OH -(aq)

1) Ammonia (:NH3)
2) Amines (general formula RNH2, R2NH, R3N), such as CH3CH2NH2, (CH3)2NH,
(C3H7)3N, and C5H5N
The Meaning of Ka, the Acid Dissociation Constant
Ka is the equilibrium constant of the ionization reaction of a weak acid.

Kb represents the ionization constant of a base.

Kw = [H3O+][OH-] = 1.0 x 10-14 (at 25°C)
 The pH Scale

• The pH is defined as the negative logarithm in base 10, of the hydronium

ion concentration
• pH = - log[H3O+]
• The pOH is defined as the negative logarithm in base 10, of the hydroxyl ion
concentration
• pOH = - log[OH-]

pH of an acidic solution < 7.00

pH of a neutral solution = 7.00

pH of a basic solution > 7.00

 Calculating [H3O+], pH, [OH-], and pOH

Strong acid (or Weak acid (or Strong and weak acid
base) base) (or base)

[H+] = acid calculate [H+] from [H+] is generally equal to

concentration Ka strong acid (effect of weak
acid neglect unless strong
acid is too dilute)
question : What is the pH of a solution that contains 10-2
M hydronium ion ?

question : Calculate the [H3O+], pH, [OH-], and pOH of

0.0024 M hydrochloric acid solutions at 25°C.
• question : The weak acid hypochlorous acid is formed in
bleach solutions. What is the [H3O+] of a 0.125 M HClO
solution? Ka = 3.5 x 10^-8
 Buffer solution
• is a solution whose pH changes only very slightly
upon the addition of small of either an acid or a base.

• Buffer solutions contain a weak acid and its conjugate

base ( its salt) or a weak base and its conjugate acid
( its salt).
• question : calculate the the pH of a buffer solution containing
0.246 M NH3 and 0.0954 M NH4Cl (for NH3 Kb = 1.74x
10-5)
• NH3 +H2O  NH4+ + OH-
 Salts of the weak acids (or weak bases) react with water
Hidrolysis to form the weak acid (or weak base).

Salt + Water ↔ weak acid + OH -

equilibrium constant of this reaction is Kh=Kw/Ka

the pH of the solution can be calculated from Kh.

question: calculate the ph of the 0.01 M sodium acetat solution.

For acetic acid, Ka= 1.8x10-5
 Polyprotic Acids
Phosphoric acid:
A triprotic acid.

H3PO4 + H2O ↔ H3O+ + H2PO4- Ka = 7.1x10-3

H2PO4- + H2O ↔ H3O+ + HPO42- Ka = 6.3x10-8

HPO42- + H2O ↔ H3O+ + PO43- Ka = 4.2x10-13

Ionization Constants of Some Polyprotic Acids
 Phosphoric Acid
• Ka1 >> Ka2
• All H3O+ is formed in the first ionization step.

• H2PO4- essentially does not ionize further.

• Assume [H2PO4-] = [H3O+].

• [HPO42-] ≈ Ka2 regardless of solution

molarity.
Calculating Ion Concentrations in a Polyprotic Acid Solution.
For a 3.0 M H3PO4 solution, calculate:
(a) [H3O+]; (b) [H2PO4-]; [HPO42-] (d)
[PO43-]
H3PO4 + H2O ↔ H2PO4- + H3O+

Initial conc. 3.0 M 0 0

Changes -x M +x M +x M
Eqlbrm conc. (3.0-x) M xM xM
 Acid Base titrations

A titration in which the reaction between the analyte and titrant is

an acid–base reaction.

Standard acid–base titrations were conducted using H2SO4, HCl, and

reactants: HNO3 as acidic titrants, and K2CO3 and Na2CO3 as basic
titrants.
Indicator : A colored compound whose change in color signals the end point of a
titration.
End points were determined using visual indicators such as litmus,
which is red in acidic solutions and blue in basic solutions,
Acidimetry: Determination of the Base content of a sample by titrating strong acid solution.
Diluted solutions of HCl, H2SO4, HClO4 are used as a titrant. Since HNO3
gives some extra reactions, it can not be used for acidimetry.
Alkalimetry: Determination of the acid contents of a sample by titrating with a strong base
solutions like NaOH, KOH ve Ba(OH)2
 Visual Indicators for Acid-base Titrations
an acid–base indicator are the weak organic acids. the weak acids
and bases derivatives of organic dyes can serve as a useful means
for determining the end point of a titration. Because such
compounds have at least one conjugate acid–base species that is
highly colored,

Indicator A colored compound whose change in color signals the

end point of a titration.

an acid–base indicator changes color with in changing the pH of the

solution.
In general terms a visual indicator is a compound which changes from one colour
to another as its chemical form changes with its chemical environment

If the indicator is present in an environment where a

titration reaction generates or consumes the X species,
the indicator will change with the concentration of X in
the solution and the colour of the solution will be
determined by the ratio [InB]/[InA]. As a general guide,
the eye will register a complete change from one colour
to the other when this ratio changes from 10:1 to 1:10.
The pH at which an acid–base indicator changes color is determined by
its acid dissociation constant. For an indicator that is a monoprotic weak
acid, HIn, the following dissociation reaction occurs

HIn(aq) + H2O(l)↔H3O+(aq) + In–(aq)

For example, the acid-base indicator methyl orange has a pKIn of 3.7 and will thus
change colour over the pH range 2.7–4.7.

The ultimate sharpness of the end point will further depend upon the rate at which pX
is changing at the end point of the titration.
 Acid-base Titration Curves
titration curve: A graph showing the progress of a titration as a function of the
volume of titrant added.

A titration curve provides us with a visual picture of how a property, such as pH, changes as
we add titrant
Titrating Strong Acids and Strong Bases

Titrating a Titrating a Titrating a Weak Titrating a Weak

Strong Base with StrongAcid with a Acid with a Strong Base with a Strong
a Strong Acid Strong Base Base Acid
 Titration Curves

Titrating a Strong starts with a low pH, then pH changes less till
Acid with a Strong equivalent point then there will be sudden change
Base (increase) at the equivalent point.

Titrating a Strong The curve starts at the basic region, till equivalent point
Base with a Strong pH decrease less but at the equivalent point sudden
Acid change (decrease) will occur.
 Titration Curves

Titrating a Weak Acid

with a Strong Base

Titrating a Weak Base

with a Strong Acid
the titration curve when titrating a diprotic weak acid, H2A,
with a strong base.
 pH Calculations in the Titrating of a Strong Acid with a
Strong Base

Before equivalence
point
At the equivalence
point
After equivalence
point
question: 50.0ml 0.050 M HCl solutrion is being titrated with 0.100
M NaOH, calculate the pH when

0 ml base added,
10 ml base added, 20ml base added,
25ml base added,
30 ml base added, and 40 base added,

Draw the titration curve.

 pH Calculations in the Titrating of a weak Acid with a Strong Base

Buffer solution A solution containing a conjugate weak acid/weak base pair

that is resistant to a change in pH when a strong acid or
strong base is added.
Buffer capacity is the mol number of a stronge acid or base needed to add for
changing the pH 1,0L solution in 1 unit
The pH of a buffer changes within the range of pH = pKa ± 1

Question: calculate the the pH of a solution containing 0.246 M NH 3 and 0.0954

M NH4Cl (for NH3 Kb = 1.74x 10-5)
NH3 +H2O  NH4+ + OH-
 Titrating of a weak Acid with a Strong Base

Salts of the weak acids (or weak bases) react with water
Hidrolysis to form the weak acid (or weak base).

Salt + Water ↔ weak acid + OH -

equilibrium constant of this reaction is Kh=Kw/Ka

the pH of the solution can be calculated from Kh.

Question : calculate the pH of a 0.01 M sodium acetat solution.

Ka= 1.8x10-5
 pH Calculations in the Titrating of a weak Acid with a Strong
Base

Adding 0ml base Calculate the pH from Ka of the weak acid

Before the Calculet the pH of the buffer solution
Equivalence point
At the Equivalence Calculate pH of the salt of the weak acid (Hydrolysis)
point
After the Equivalence Calculate the pH from the concentraion of the base (not
point consumed in the reaction)
Soru: 50ml 0.10 M acetic acid is being titrated with 0.10 M NaOH. calculate the
pH when.

0ml base added ,

10 ml base added
45 ml base added
50 ml baz ilavesi
51 base added 55 ml base added

Ka= 1.8x10-5
 Titrasyonda İndikatörden gelen Hatalar

Belirli hatalar Rastgele hatalar

indikatörün renk değişim pH renk değişimi izlenirken göz

aralığının titrasyonun eşdeğerlik yanılgılarından kaynaklanır.
noktasındaki pH ının faklı olması
sonucu olur. Uygun indikatör seçimi,
tanık deney düzeltmesi ile azaltılır.
 complexometric titrations

A complexometric titration is based on the essentially stoichiometric reaction of a

complexing agent with another species to form a complex species that is only
slightly dissociated and that is soluble in the titration medium.

Complex The product of the complexation reaction is called a metal–ligand

complex.

Ligant A Lewis base that binds with a metal ion

Chelat bir metalin bir ligantla bağlanarak oluşturduğu halkalı kompleks tir

formation The equilibrium constant for a reaction in which a metal and

constant a ligand bind to form a metal–ligand complex (Kf).
EDTA The most widely use ligands is ethylenediaminetetraacetic
acid, EDTA, forms strong 1:1 complexes with many metal
ions.
Dissosiation constants of EDTA:
K1= 1.02x10-2 K2= 2.14x10-3 K3= 6.92x10-7 K4= 5.50x10-11
 EDTA çözeltilerinde α değerlerinin hesaplanması
EDTA Hidrojen iyonlarını kaybederek [Y4- ]+[HY3-]+[H2Y2-]+[H3Y-]+[H4Y]
şu türlere iyonlaşır K1= 1.02x10-2 K2= 2.14x10-3
K3= 6.92x10-7 K4= 5.50x10-11
Y4- nin çözeltideki [Y4-]
mol kesri α4= --------------
CEDTA
CEDTA= [Y4- ]+[HY3-]+[H2Y2-]+[H3Y-]+[H4Y]
Buradan K1K2K3K4
K sabitleri α4= -------------------------------------------------------------------------
kullanılarak [H+]4 + K [H+]3-+ K K [H+]2- + K K K [H+] + K K K K
1 1 2 1 2 3 1 2 3 4

K1K2K3K4
α4 = ------------------------------ olarak bulunur
CEDTA
EDTA Metal İyonları Kompleksleri
Mn+ + Y4- ↔ MYn-4 [MYn-4 ]
KMY = ------------------
[Mn+] [Y4-]
[MYn-4 ]
K’MY (durum sabiti) K’MY = ----------------- = α4 KMY
Calculate the Concentration of Ni2+ in a soltion which
prepared as mixing 50.0ml 0.0300 M Ni2+ and
50.0mlml 0.0500 M EDTA at pH= 3
At pH=3 , α4= 2.5x10-11 KNiY=4.2x1018
 EDTA titrasyon eğrileri
Verilen pH değeri için durum sabiti değeri bulunur hesaplamalarda
kullanılır.
Eşdeğerlik ortamda metal iyonu fazlası vardır ve
noktası öncesinde harcanmadan kalan metal iyonu
konsantrasyonu hesaplanır.
Eşdeğerlik ortamda sadece kompleks vardır ve bir miktar
noktasında ayrışır, ayrışan metal iyonu konsantrasyonu
durum sabitinden hesaplanır.

Eşdeğerlik EDTA fazlası vardır ve artan EDTA

noktası konsantrasyonu durum sabitinde yerine
sonrasında konarak metal iyonu konsantrasyonu
hesaplanır.
50.0ml 0.0500 M Mg2+ nın 0.0500 M EDTA ile
titrasyonunda pH=10 na tamponlanıyor,
0ml, 5.0ml, 50.0ml ve 51.0 ml EDTA ilaveleri için
Mg2+ konsantrasyonunu hesaplayınız ve titrasyon
eğrisini çiziniz.
PH=10 için α4= 3.5x10-1 Kol= 6.2 x 108
 EDTA titrasyonları için İndikatörler

Genel olarak metal iyon indikatörleri kullanılır. Bunlar metal

iyonlarına bağlandığında renk değiştiren organik boyalardır.
MetalIn + EDTA → MetalEDTA + In
Renk 1 renksiz renksiz renk 2
Chelometric titrations may be classified according to their manner of performance: direct
titrations, back titrations, substitution titrations, or indirect methods.

direct back titrations substitution indirect methods

titrations titrations
0,300 g metal wire is being dissolved in nitric acid and diluted to 100,0ml with pure
water. 25.00ml sample is taken from this solution and added 0.052 M EDTA and
then neutralized with NaOH. After that the pH of the solution is buffered to pH=5.5.
and excess EDTA is back titrated with 17.61ml 0.02299M Zn 2+. Calculate the Ni2+
percent in the metal wire. (Ni: 58,71g/mol EDTA:372,0g/mol)
 Application of Equilibrium Calculations to Complex Systems

when aqueous solutions contain several species that interact with one
another and water that yield two or more simultaneous equilibria.

PbS ↔ Pb2+ + S2-

S2- + H2O ↔ HS- + OH-
HS- + H2O ↔ H2S + OH-
2 H2O ↔ H3O+ + OH-
 Steps for solving problems involving several equilibria

1. Write all chemical equations and balance them

2. Write all equilibrium constant wxpressions.
3. State (undrline) which quantity (unknown) you want to find
(solve).
4. Write mass balance expression for the system.
5. Write the charge balance equation (IF possible)
6. Compare the number of equations and the number of
unknowns.
7. Make suitable approximations to simplify the algebra.
8. Solve the algebraic equations, find the unknown defined at
step 3.
9. Check the validity of approximations.
mass balance equation: (which is simply a statement of the conservation of matter.)
An equation stating that matter is conserved, and that the total amount of a
species added to a solution must equal the sum of the amount of each of its
possible forms present in solution.

charge balance equation: (is a statement of solution

electroneutrality.) An equation stating that the total concentration of positive
charge in a solution must equal the total concentration of negative charge.
Total positive charge from cations = total negative charge from anions.
Write the mass balance equation for 1 liter of 0.250mol H 3PO4
aqueous solution.

Write charge balanse equation for a solution which contains

H+, OH-, K+, H2PO4-, HPO42- and PO43-
Calculate the Hg22+ cocentration in a saturated Hg2Cl2 solution.
Ksp= 1.2x10-18 Kw=1x10-14
 Calculate the molar solubility of Mg(OH)2 in water.

Ksp Mg(OH)2 = 7.1x10-12 Kw=1x10-14

Calculate the molar solubility of Fe(OH)3 in water.

Ksp Fe(OH)3 = 2.0x10-39 Kw=1x10-14

Calculate the solubility of calcium oxalate in a solution which
the Hydronium ion cocentration is 1.0 x 10-4

For CaC2O4 Ksp= 2.3 x 10-9

for H2C2O4 Ka1= 5.36 x 10-2, Ka2= 5.42 x 10-8
Kw=1x10-14
Calculate the solubility of AgBr in 0.1 M NH3 solution.

For AgBr Ksp= 5.2 x 10-13

for Ag(NH3)+ Kformation oluşum= 2 x 103
for Ag(NH3)2 Kformation= 6.9 x 103
for NH3 Kb= 1.76 x 10-5
 Soru: 0.1 M Pb2+ ve 0.1 M Fe2+ içeren bir çözeltiye H2S
eklenerek Pb2+ ve Fe2+ iyonları birbirinden ayrılması için
gerekli koşulları belirleyiniz. Kçç(PbS)=3x10-28,
Kçç(FeS)=8x10-19 H2S için K1=9.6x10-8 K2=1.3x10-14
Calculate the solubilty of HgS in water by using all equations
which occur.

for HgS Ksp = 5 x 10-54

Kw= 1.0 x 10-14,
for H2S Ka1= 9.6x10-8 Ka2= 1.3x10-14