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Analisis titrimetri

titrasi asam basa.

Hal yang akan dipelajari


1.
2.
3.
4.
5.
6.
7.

Metoda Titrimetri : konsep dasar dan klasifikasi.


Teknik dr titrimetri analisis.
Tipe dr penentuan titrimetri
Perhitungan dalm analisis titrimetri
Titrasi asambasa (metoda neutralisasi): konsep
dasar, titran, definisi substances.
Pemilihan Indikator perhitngan kesalah dlm titration.
Titrasi asam basa dlm pelarut non air

1. Metoda analisis Titrimetri : konsep


dasar dan klasifikasi.
Titrimetri suatu metoda dimana volume
merupakan signal.
Titrimetri, kita mengukur sejumlah volume dr
reagen yang breaksi secr stoikiometri dgn
analit.

Prinsip dasar metoda


titrasi :
1.
2.
3.
4.

Reaksi harus stoikiometri


Reaksi harus berlangsung cepat
Tidak ada reaksi samping
Harus terjadi perubahan ketika reaksi
telah sempurna. (indikator)
5. Terdapat titik ekuivalen
6. Reaksi harus kuantitatif

Rangkaian Titrasi : titran ditambhkn dr buret ke lart analit dalam gelas


erlenmeyer. Adanya indikator menunjukkan perub warna secr
permanen yg menunjukkn titik akhir.

Titrasi larutan asam yg tdk diketahui konsentrasinya degn


larutan basa yg diketahui secara pasti konsentrasinya

Titration adl suatu prosedur penentuan konsentrasi suatu


larutan dengan membiarkan sejumlh tertentu volume
bereaksi dengan suatu larutan standard yang
konsentrasinya telah diketahui secara pasti.
Standardisasi adalah suatu proses memastikan suatu
teknik standar
In chemistry, aliquot adlh toatal jumlah suatu larutan.

Titrant - the reagent added to a solution containing the


analyte and whose volume is the signal.
A reagent, called the titrant, of known concentration (a
standard solution) and volume is used to react with a
solution of the analyte, whose concentration is not
known.
equivalence point titik ketika terjadi stoikiometri /
reaksi berjalan ekuivalen antara sejumlah analit dan titran.

End point - the point in a titration where we stop adding


titrant.
Indicator - a colored compound whose change in color
signals the end point of a titration.
Titration error - the determinate error in a titration due to
the difference between the end point and the equivalence
point.
standar primar mrpk suatu standar (material) sangat
murni yang tidak perlu dikalibrasi oleh standar lainnya.

Standar Sekunder suatu reagen yang kemurniannya


harus dipastikan terhadap standar/reagen primar.
A burette (also buret) is a vertical cylindrical piece of
laboratory glassware with a volumetric graduation on its
full length and a precision tap, or stopcock, on the
bottom (or calibrated glass tube).
Even the thickness of the lines printed on the burette
matters; the bottom of the meniscus of the liquid should
be touching the top of the line you wish to measure from.

stopcock buret

Buret dengan botol berisi larutan standar

Buret Gay-Lussac

Buret
shutter

Buret Mohr

with

rubber

Microburet:
) Shilov air-powered Buret; ) stopcock buret

Pipet (juga disebut pipet, pipettor or chemical


dropper) adl suatu instrumen laboratori yg
digunakan untuk memindahkan sejumlh volume
larutan

Gelas Erlenmeyer

Terdapat bbrp cara utk menyiapkan


larutan standar :
Menimbang sample secra accurat (primar
standar)
by means of standard substance or a
standard solution (secondary standard)
standard titrimetric substance (primary
standard)

Accurately weighed sample (primary


standard)
Karena glas volumetri berisi suatu larutan, sangat penting
untuk menyiapkan larutan dengan konsentrasi yg eksak.
Reagent (the accurately weighed sample) dipindahkn ke
glas volumetri, dan sejumlh pelarut ditambhkn utk
melarutkn reagen. Setelah semua reagent terlarut, pelarut
ditambhkan secara proporsional sampai tercapai volume
secara fix. The final adjustment of volume to the flasks
calibration mark is made using a dropping pipet. To
complete the mixing process, the volumetric flask should
be inverted at least ten times.

Volumetric flask

Volumetric flask for preparing


liquids with volumes of high precision.
It is a flask with an approximately
pear-shaped body and a long neck with
a circumferential fill line.

Cara membaca meniskus pada volumetric flask


or pipet.

Jika mengisi pipet or volumetric flask, atur cairan secra tepat pada daerah
kalibrasi. The liquids top surface is curved into a meniscus, the bottom of
which should be exactly even with the glasswares calibration mark. The
meniscus should be adjusted with the calibration mark at eye level to avoid
parallax errors.

Perhitungan konsentrasi standar primer


m
C
MV
M

m
C
N E V
m

T m/V

by means of standard substance or a


standard solution (secondary standard)
secondary reagent - a reagent whose purity
must be established relative to a primary reagent
To prepare the solution we place calculated
amount of substance, weighed to the nearest
tenth of a gram, in a bottle or beaker and add
approximately volume of water

Memastikn konsentrasi standar sekunder


) mengukur volume dr larutan
standar primer lain

CN 2

C N1 V1

V2

where:
CN2 and V2 are concentration and volume
of secondary standard solution
CN1 and V1 are concentration and volume
of primary standard solution

B) Menimbang sejumlh tertentu standar primer

CN

m 1000

Em V

where:
CN and V are concentration
and volume of secondary standard
solution
m and Em are mass and
equivalent weight of primary
standard

Typical
instrumentation for
performing
an
automatic titration.
Courtesy of Fisher
Scientific.

Suatu standar primar harus :


1. Hrs merupakn crystal structure and berhubungan
dgn formula kimia
2. High purity (it is the absence of impurity in a
substance)
3. Stability (low reactivity), baik pada suhu kamr or
ketika dipanaskan.
4. Low hygroscopicity and ef-florescence (in chemistry,
is the loss of water (or a solvent) of crystallization
from a hydrated or solvated salt to the atmosphere on
exposure to air).

5. High solubility (if used in titration)


6. High equivalent weight.
7. Not to contain extraneous impurity more than
admissible borders for substances of mark
chemically pure.
8. Methods of purification of standard substance from
impurity (crystallisation, extraction, sublimation
etc.) should be available in analytical laboratory.

Beberapa conto st primar (European Pharmacopoeia) :


Arsenic trioxide ArO3 utk mbuat sodium arsenite solution
for standardisation of sodium periodate solution (also for
iodine and cerium (IV) sulfate solutions, since 2002
standardised by sodium thiosulfate)
Benzoic acid for standardisation of waterless basic
solutions: Na- etanolat and KOH, TBAH, and alkali
metanolat dlm metanol, isopropanol, or DMF
Potassium bromate (KBrO3) for standardisation of Nathiosulfate solutions

Potassium hydrogen phthalate (KHP) for standardisation


of aqueous base and asam perklorat dlm lart as. Asetat
Na2CO3 for standardisation of aqueous acids: HCl,
H2SO4 and H2NO3 solutions (but not acetic acid)
NaCl for standardisation of larutan AgNO 3
Asam Sulfanilat for standardisation of NaNO 2
Zinc powder, after being dissolved in sulfuric or
hydrochloric acid, for standardisation of EDTA solutions

standard titrimetric substance


(primary standard)
More often in an
ampoule contains 0,1
mol (0,1 equivalents)
of substances, it is
necessary
for
preparation of 0,1
mol/L solution.

Preparation rules primary solutions


and definition of their titre.
1. The initial substance which is used for
preparation of a standard solution, should be
chemically pure.
2. The initial substance should easily and quickly
react with standartized solution.
3. The solution of initial substance dont change
itself concentration long time.
4. It is necessary to use reactions between initial
and defined substance, which are possible in
direct titration.

5. Titration process should end quickly and


accurately. The end point of titration should will be
defined easily and precisely.
6. To establish of titre it is desirable either a method
of accurately weighed sample or dissolution of
precisely weighed initial substance in certain
volume.
7. For the prevention of errors by titration it is
necessary to choose volume of the primary
standard aliquot or weighed of standard substance,
that the volume of the secondary standard which
will react in titration was not less than 20 mL (buret
on 25 mL) or 40 mL (buret on 50 mL).

8. Titration should be carry out until then it will not be


received yet three reproduced results.
9. Prepared of standartized solution should be stored in
conditions which exclude absorption of air moisture
by them, and also evaporation. A titre should not
change at standing in time.
10.Wares and measuring devices which are used in
titrimetry, should be washed up, calibrated, prepared
for titration and should be stored in a pure place.
11.Accuracy measurement of volumes and the
calculations, should correspond to accuracy of
weighing.

Metoda titrimetri dibagi menjadi 4 tipe.


acidbase titrations, in which an acidic or basic
titrant reacts with an analyte that is a base or an acid;
complexometric titrations involving a metalligand
complexation reaction;
redox titrations, where the titrant is an oxidizing or
reducing agent;
precipitation titrations, in which the analyte and
titrant react to form a precipitate.

Requirements to reactions in titrimetric analysis

all reactions involving the titrant and analyte must be of


known stoichiometry, quantitatively
the titration reaction must occur rapidly
a suitable method must be available for determining the
end point with an acceptable level of accuracy
Reactions should proceed by room temperature
Titration should not be accompanied by collateral
reactions which deform the results of the analysis
Reactions should be specific

2. Techniques of titrimetric analysis.

Washing up and drying ware


Preparation of standard solutions
Sample preparation
Titration:
- Measurement of volumes
- An indicator choice
Calculations

Contoh umum glassware yg digunakan utk mukur


volum :

beaker

volumetric flask
Graduated cylinders

transfer pipet;

measuring pipet

Calibration: volumetric flask - an injection method


pipettes, burettes - a pouring out method

Methods to determine the end point


visual indicators:
Colour change: In some reactions, the solution changes colour without
any added indicator. This is often seen in redox titrations, for instance,
when the different oxidation states of the product and reactant produce
different colours.
Precipitation: If the reaction forms a solid, then a precipitate will form
during the titration. A classic example is the reaction between Ag + and
Cl- to form the very insoluble salt AgCl. This usually makes it difficult
to determine the endpoint precisely. As a result, precipitation titrations
often have to be done as "back" titrations (see below).
Physical and chemical methods with the subsequent analysis of curves
of the titration showing changes which occur in the course of titration
(change of physical and chemical parametres standard solutions)

3. Tipe penentuan dlm titrimetri.


Titration can be:

direct titration
back-titration (on residue)
substitute-titration (displacement titration)
revertive titration

direct titration titrant add to an analyte solution and react with


determined substrance

Requirements to reactions in direct titration


reaction involving the titrant and analyte must be of
known stoichiometry, quantitatively
the titration reaction must occur rapidly
a suitable method must be available for determining the
end point with an acceptable level of accuracy
Reactions should proceed by room temperature
Titration should not be accompanied by collateral
reactions which deform the results of the analysis
Reactions should be specific
a suitable indicator is available
+ = product

Back titration. A titration in which a reagent is added to a


solution containing the analyte, and the excess reagent
remaining after its reaction with the analyte is determined
by a titration.
This titration is used, when:
the titration reaction is too slow,
a suitable indicator is not available,
there is no useful direct titration reaction
the standard solution lacks of stability (fugitive)
+ excess = product1 + residue
residue + padding = product2

displacement titration. A titration in which the analyte


displaces a species, usually from a complex, and the amount
of the displaced species is determined by a titration.

This titration is used, when:


the analytes are unstable substance
It is impossible to indicate the equivalent (end) point in direct
reaction
Analyte doesnt react with titrant
reaction involving the titrant and analyte mustnt be of known
stoichiometry, quantitatively

+ 1(padding compounds) = 1(substituent)


1(substituent) + = product
CrCl2 + FeCl3 = CrCl3 + FeCl2
analyte
substitute
5FeCl2 + KMnO4 + HCl = 5FeCl3 + KCl + MnCl2 + 4H2O

Revertive titration.
A standard solution is titrated by solution of
investigated substance in reversive titration

(in burette) + (in flask) = product

4. Calculations in titrimetric analysis.

Weight of investigated substance by results of direct, displacement or


reversive titration:

C K V E V
m
1000 V
H

T K V V
m
V
T A

Weight of investigated substance by results


of back titration:

(C K V C K V )E V
m
1000V
H1

T1

H2

T2

Titre of titrant by investigated substance:

(T) E ( A )

1000

5. PROTOLYTOMETRY OR ACIDBASE TITRATION (A


NEUTRALIZATION METHOD): THE BASIC CONCEPTS,
TITRANTS, DEFINED SUBSTANCES.

Acidbase titration - titration in which the reaction


between the analyte and titrant is an acidbase reaction.
Protolytometry is titrimetric method of analysis which uses
solutions of acids or bases as titrants. In this method of the
analysis defined substances are the substances, capable to
react with acids and the bases.
The basic reaction of a method:
+ + - = 2 or
HA + B = BH+ + A-

Methods of acid-base titration or acidbase titrimetry:

acidimetry (titrants - HCl, H2SO4)


alkalimetry (titrants - NaOH, KOH)
All titrants are secondary standard solutions,
therefore demand of standardization
(definition of precise concentration).

Standardization of acidic titrants - solutions of


acid HCl, H2SO4
Standard (reference) substances sodium
tetraboratic
Na2B4O75H2O
or
Na2B4O710H2O, sodium carbonate Na2CO3:
Na2B4O7 + 2HCl + 5H2O = 2NaCl + 4H3BO3
Na2CO3 + 2HCl = 2NaCl + CO2 + H2O

Standardization of l solution on sodium tetraborate.

Weigh exact shot of Na2B4O75H2O or


Na2B4O710H2O and place it in a measured flask,
dissolve in hot water, after a solution is cooled
and diluted of solution by water to necessary
volume and it is mixed.
In a flask for titration place an aliquot of
prepared
primary
standard
solution
Na2B4O75H2O or Na2B4O710H2O, add some
drops of the methyl orange. The received solution
is titrated by solution of l to change of colour
with yellow to orange with a rose shade.

Standardization of l solution on sodium


tetraborate.
By 3-4 results of titration calculate average volume of used titrant
and calculate concentration of hydrochloric acid.

CN HCl

CN Na B O V
2 4

VHCl

Na2 B4O7

Standardization of HCl solution on sodium carbonate


In a flask for titration place exact shot of sodium
carbonate, dissolve in necessary volume of water, add
some drops methyl orange and titrate this solution by
chloric acid.
Such titration repeat for 3-4 times. Each time calculate
concentration of HCl:

CN _ HCl

mNa CO 1000
2

EmNa CO VHCl
2

By 3-4 results of titration


concenration of chloric acid.

calculate

average

Standardization of basic titrants - solutions of bases of


NaOH, KOH

Standard (reference) substances oxalate


acid
H2C2O42H2O,
succinate
acid
H2C4H4O4:
H2C2O4 + 2NaOH = Na2C2O4 + 2H2O
H2C4H4O4 + 2NaOH = Na2C4H4O4 + 2H2O

Standardization of NaOH solution on oxalic acid.


Weigh exact shot of H2C2O42H2O and place it
in a measured flask, dissolve in hot water, after
a solution is cooled and diluted of solution by
water to necessary volume and it is mixed.
In a flask for titration place an aliquot of
prepared
primary
standard
solution
H2C2O42H2O , add some drops of the
phenolphthalein. The received solution is
titrated by solution of NaOH to change of
colourless to rose (or red).

Standardization of NaOH solution on oxalic acid.


By 3-4 results of titration calculate average volume of used
titrant and calculate concentration of NaOH.

C N _ NaOH

CN H C O V
2

VNaOH

H 2C2O4

According to force of acid and the base such


types of the acid-base interaction are possible:
Between strong acid and the strong basis
NaOH + HCl = H2O + NaCl
Between weak acid and the strong basis
NaOH + CH3COOH CH3COONa + H2O
Between strong acid and the weak basis
NH4OH + HCl = NH4Cl + H2O
Between weak acid and the weak basis
CH3COOH + NH4OH = CH3COONH4 + H2O

6. INDICATOR CHOICE, CALCULATION OF ERRORS


OF TITRATION IN A METHOD PROTOLYTOMETRY.

Indicators of acid-base titration


The substances which colouring changes depending on size
change of solution.
Requirements to indicators:
Indicator colouring at near values should differ well
Change of colouring of the indicator should occur sharply in a
small interval of
Indicator colouring should be as it is possible more intensively
The quantity of base or acid, necessary for change of
colouring of the indicator, should be very small
Change of colouring of the indicator must to be reversible

1894 the ionic theory of indicators

Indicators of an acid-base titration method


are weak acids or the bases at which not
ionised molecules and ions have different
colouring
HInd
red

Lacmus
Phenolphthalein colourless

H+

Indblue
rose

Ind: - one-colour (phenolphthalein )


- two-colour (methyl orange , lacmus)

Limitation of ionic theory of indicators :


Ascertaining of different colouring of acidic
and basic forms, but is not present an
explanation of presence and colouring change.
The structure and colouring are not connected.
Colouring change is ionic process but why it
often is long in time?
Advantages of the ionic theory: possibility of
quantitative interpretation of results of change
of colouring.

The theory of chromophore colouring of organic


compounds is connected with presence of a
chromophore groups at molecules of indicators :

- N=N-; -N=O; =C=S; -N=NO

Auxochrome groups havent colouring, but with


a chromophore groups strengthen action of the
last, causing deeper intensity of colouring.
C2H5

CH3
-OH; -NH2; -OCH3;

N
CH3

N
C2H5

Colouring change is a consequence of isomeric


transformation which changes an indicator
structure
N

O
O

OH

The colourless form

O N-O-H

The yellow form

Limitation of chromophore theory of indicators


Does not give an explanation why tautomeric
transformations and change of colouring of a
solution of indicators occurs at change a
solution.
Colouring changes instant, where as intramolecular transformations generally long
processes is frequent.
Does not give a quantitative estimation of
connection of colouring change with change .

The ionic- chromophore theory


The acid-base indicators are weak acids and the
bases, and the neutral molecule of the indicator
and its ionised form contain different
chromophore groups
N

O
O

O N-O-H

N-O
O

+ H+
OH

colourless

yellow

yellow

The ionic- chromophore theory

1
2
Ind0 HInd H+ + Indthe acid
the base
form
form

acid . form
pH pK lg
base. form

pH pK 1

of most often used indicators in the acid-base


titration:
Methyl orange
4,0
Methyl red
5,5
Lacmus
7,0
Phenolphthalein
9,0
pT of the indicator is value of at which colour
of the indicator sharply changes and stop to add
titrant (there is end point of titration)

Factors which influence the indicator indication.


At increase t the temperature indicator becomes
less sensitive to + -ions for indicators-bases
Presence of organic solvent (alcohol, acetone),
albuminous molecules, salts changes of the
indicator
It is necessary to define titre a working solution
in the same conditions at which the test analysis
is conducted
it isnt recommended to take a lot quantity of
indicator

2. Indicator

choice, calculation of errors of


titration in a method protolytometry.
Indicator choice spend two methods:

On reaction products
On titration curves

Titration curve for 0,1 mol/L hydrochloric acid by 0,1


mol/L sodium hydroxide

Dependence of inflection points on concentration of


defined substance
(0,1 mol/L and 0,01 mol/L)

Dependence of inflection points


on force of acid

Dependence of inflection points


on force of acid

Titration curve for weak acid (CH3COOH) by


weak base (NH4OH)

Titration curve for H3PO4 by NaOH

Factors which influence on


inflection points

constants of acid or base


temperatura of solutions
concentration of defined substances
concentration of used titrants

Choice of the indicator:


The pT of indicator (interval of transition of colouring
- pH range) should be in limit of inflection points on a
titration curve

Choice of the indicator:


The pT of indicator (interval of transition of colouring
- pH range) should be in limit of inflection points on a
titration curve

Titration curve of 0.100 M HCl


with 0.200 M NaOH

Titration curve of 0,1 CH3COOH


by 0,2 M NaOH

Titration curve of 0,1 NH3


by 0,1 M HCl

Titration curve of weak acid by weak base

Titration curve for 50.00 mL of 0.100 M CH3COOH


with 0.100 M NaOH showing the range of pHs (or pT)
and volumes of titrant over which the indicators
bromothymol blue and phenolphthalein are expected to
change
color.

Titration curve of mix


0,1 M HCl + 0,1 M CH3COOH
by 0,1 NaOH

Acetic acid
=1,7410-5

Titration curve of mix


acetic and malatic acids
Malatic acid
=1,5010-4
Acetic acid
=1,7410-5
1:2<104

Titration curve of maleinic acid

Titration curve 0,1 oxalic acid


by 0,1 NaOH

Determinate the end-point by potentiometric way

Titration error - the determinate error in a titration due


to the difference between the end point and the
equivalence point.
Indicators error

+ if have excess of base when define


acid
- if have rest of acid when define acid
Hydroxonium error
pT

10 V2
x
100%
Ck Vk

Indicators error :
Hydroxyl error

Acidic error

Bases error

pT 14

10
V2
x
100%
Ck Vk
x HA 10

xMeOH 10

100%

b 14

100%

7. NONAQUEOUS ACIDBASE TITRATION.


Titration in water solutions is limited by factors:
It is impossible to titrate for a mix of acids or the
bases if constants of dissociation differ less, than
on four order
It is impossible to titrate for a mix of strong and
weak acids (bases)
It is impossible to titrate very weak acids (bases)
It is impossible to titrate separately for a mix of
acids (bases) with near constants of dissociation
It is impossible to define substances which are
insoluble in water.

Choice of solvents:

The constant of autoprotolysis solvent should be


as small as possible
For titration of the weak bases should be to take
a solvent with the expressed progenic properties
(the acid nature of solvent)
For titration of weak acids should be to take a
solvent with expressed protophilic properties,
(the basis nature of solvent)
Dielectric inductivity of solvent should be as it
is possible above

The weak bases often are titrated in the acetic acid


medium
(strengthening of force of the bases)
Titrant: perchlorate acid HClO4
Standardization: on potassium hydrogenphthalate,
or on sodium salicylate if have solution of HClO4 in
CH3OH

Nonaqueous acidbase titration of weak bases by


perchlorate acid

Indicators: crystal violet (violet blue or


green),
thymol dark blue (yellow rose).

The weak acids often are titrated in the medium


dimethyl formamide, ethylene diamine, butylamine,
pyridine
(strengthening of force of the acids)

Titrant: sodium hydroxide NaOH in the


solution of benzene with methanol
sodium methylate CH3ONa in
methanol or in the solution of benzene with
methanol.

Standardization of NaOH and CH3ONa on


benzoic acid

Nonaqueous acidbase titration of weak


acids by NaOH or CH3ONa
Indicators: thymol blue (red-yellow and
yellow-blue) or physico-chemical methods
(potentiometry).

In nonaqueous acidbase titration determinate


the end-point by potenthiometric way

In nonaqueous acidbase titration determinate


the end-point by potenthiometric way

Thanks for your attention!