OFFICIAL LABORATORY REPORT

ENVIRONMENTAL CHEMISTRY

STANDARDIZE A SECONDARY SOLUTION

FROM PRIMARY SOLUTION

NAME : CAHYANINGRUM AYU A.

NRP : 03211740000028
LECTURER : ARSETO YEKTI B,ST,MT,M. Phil, PhD
LABORATORYS ASSISTANT : PRIESKARINDA LESTARI

ENVIRONMENTAL ENGINEERING DEPARTEMENT

FACULTY OF CIVIL ENGINEERING, ENVIRONMENT AND GEOSCIENCE
SEPULUH NOPEMBER INSTITUTE OF TECHNOLGY 2017
1. Introduction
1.1. Objectives
a. Students are able to choose which material that can be used for primary standard solution
b. Students are able to determine the concentration of secondary standard solution
c. Students are able to correctly use laboratory apparatus and properly perform dilution
experiment

1.2. Principles
Stoichiometric reaction of primary and secondary standard reagents can be used on basic
calculation of both standard solutions. Therefore, secondary standard solution can be standardise
using mol equivalent of primary standard solution that has been used in stoichiometric reaction.
Thus, secondary solution can be standardized by calculating equivalent mol of primary standard
that is used for stoichiometric reaction.
Potassium dichromate is a powerful oxidizing agent after permanganate. This substance
(in solid form) is stable and tend to be in high purity when stored. While in liquid form is less
stable due to light intensity. On the other hand, FAS is quite stable salt. In acid condition,
dichromate acid (Cr(IV)) will be reduced to Cr(III), whereas Fe (II) will be oxidized to Fe (III).
Therefore, redox reaction has the same equivalency. FAS under acid condition will be brokedown
to ferri sulphate (FeSO4) before its reaction woth dichromate. Complete reaction in this
experiment is as follow

1.3. Literature Review

This chapter discusses the titration system. In titrimetry, unknown samples are evaluated
by adding the titrant of a known concentration. The progress of the chemical reaction is indicated
by a change of a suitable property such as a color, absorbance or potential. A state space model is
designed to estimate in potentiometry the titration curve and its derivatives. From the estimated
state, the set point and the inflection point can be evaluated offline. The discrete titration is
investigated, where the titrant is delivered in discrete volume increments and the solution is
allowed to equilibrate. The Kalman filter causes a systematic delay in the estimated state and so
in the evaluated inflection point or set point, which is completely removed by subsequent fixed-
interval smoothing. Implementation of the Kalman filter allows the online control of variable
volume additions in order to obtain equidistant measurements. For continuous titrations, the
extension of the state space model based upon first-order dynamics is proposed. The Kalman filter
allows the online control toward an empirically established endpoint in the titration curve. An
attempt to estimate in a nonlinear fashion the exponential factor simultaneously with the titration
curve and its derivatives was unsuccessful.
(P.C. Thijssen, 2010)
A new method to convert the potential of an ion-selective electrode to concentration or
activity in potentiometric titration is proposed. The advantage of this method is that the electrode
standard potential and the slope of the calibration curve do not have to be known. Instead two
activities on the titration curve have to be estimated e.g. the starting activity before the titration
begins and the activity at the end of the titration in the presence of large excess of titrant. This new
method is beneficial when the analyte is in a complexed matrix or in a harsh environment which
affects the properties of the electrode and the traditional calibration procedure with standard
solutions cannot be used. The new method was implemented both in a method of linearization
based on the Grans's plot and in determination of the stability constant of a complex and the
concentration of the complexing ligand in the sample. The new method gave accurate results when
using titrations data from experiments with samples of known composition and with real industrial
harsh black liquor sample. A complexometric titration model was also developed.
(Kim Granholm, 2015)
 Webster's dictionary gives a definition of the word titration as the process of finding
out how much of a certain substance is contained in a solution by measuring how much of another
substance it is necessary to add to the solution in order to produce a given reaction. This term has
a slightly different meaning in colloid chemistry; an obvious reaction is the change in -potential
due to additions to the chemical composition. We discuss here examples of pH titration, surfactant
titration, and salt titration. Evolution of the sample in time can be considered as kinetic titration.
There is a special section on importance of the proper sample agitation during titration and various
means of conducting such agitation.
(Andrei S. Dukhin, 2017)

This article provides extensive and exhaustive mathematical description of titration curves
related to acid-base systems with mixtures of mono- and polyprotic acids and their salts and bases
involved. The related curves are presented in compact forms facilitating further operations made
for particular needs. Some derivative properties of the curves, such as buffer capacity and inflection
points, are also discussed. The windowed (B V ) buffer capacity is interrelated with dynamic
( V ) buffer capacity, introduced for dynamic (titration) systems. The equations useful for
searching the inflection points on titration curves are derived. A kind of homogenization of
complex acid-base systems, with polyprotic acids with defined and/or undefined (e.g., fulvic acids)
composition, with use of an approach based on Simms constants principle, has been considered in
context with buffer capacity and alkalinity. The new concepts of total alkalinity (TAL) and total
acidity (TAC), unlike ones considered hitherto, has been introduced. The TAL is determined
according to curvefitting method with use of iterative computer program, applied to nonlinear
regression equation involving Simms or Hill constants. Searching the best fit of the related function
is involved with addition of consecutive hyperbolic terms.
(Tadeusz Michaowski, 2011)

Acidity levels affect water chemistry and the Chemical Reaction Networks (CRN)
encountered within it. In other words, pH is an external factor that influences speciation, precluding
or promoting the appearance of certain chemical species as shown by distribution diagrams.
Therefore, there is not a unique CRN for the entire pH spectrum. Moreover, it might be the case
that an operative CRN for a given pH interval also supports the steady states values engendered by
a second CRN which is operative for a distinct pH interval. In this sense, the first CRN is steady
state equivalent with respect to the second CRN. Due to their importance for pH regulation in water
chemistry and similarity in their speciation diagrams, we consider the well-known phosphoric acid-
calcium carbonate system as a case study to show how steady state equivalence allows us to find
relationships between reactions in speciation.
(Gonzlez, 2017)

2. Experiment Procedure
2.1. Experiment I Preparation of Primary Standard Solutions

Drying solids K2Cr2O7

Dryed oven at 105 C for 2 hours
Inserted into the desiccator

weigh K2Cr2O7 solids of 0.4903 g ( 0.0002 g)

Dissolve in beaker glass with 10 mL of distilled water

 Put into diluent flask 100 mL
Rinse beaker glass and stirrer with a little aquaduct and then put it
all into diluent flask,
Shuffle the solution well,
Add the distilled water to approximately 1-3 cm below the
dilution limit.
Dry with the inside of the neck and outside of the diluent flask.
Add the aquades by using pipette
Adding the solution to the bottom miniskus just at the boundary
mark does not pass through the wall of the flask neck.

Swirl the solution until it is completely homogeneous

Calculate the concentration of potassium chromate

solution

2.2. Experiment II (Determination of Secondary Standard Solutions)

Considering the salt of Mohr or Ferro Ammonium

Sulfate (FAS), Fe(NH4)2(SO4)2.6H2O as much as 3.92 g

Dissolve salt in beaker glass with 10 mL of aquades

Transfer into a 100 mL volumetric flask

Rinse beaker glass into the flask

Adding distilled water to approximately 75 ml
Add concentrated H2SO4 2 mL
Drain the acid on the neck wall, do not drop it.
Rinse the walls in the neck of the diluent flask until approximately
2-3 cm of solution is below the boundary mark.

Invert well and let it cool down to temperator room

aquades added by using pipette

 Dropped to the bottom miniskus just on the boundary marks, the
solution does not pass through the wall of the pumpkin neck.
Mix well into homogeneous solution
Insert the solution into the buret
Look out for no bubbles trapped in a burette until the burlet outlet
mouth

Note the initial buret volume (initial reading scale)

If possible set to zero

Take 25 mL of solution in Experiment 1 (K2Cr2O7)

Put in the erlenmeyer flask
Added H2SO4 concentrated 10 mL
Stirred for homogenization and cooled to room temperature
Added with 2-3 drops of ferroin indicator.
Titrated
with FAS solution
Stops titration when the color changes from green to brick red for
the first time

Records the final volume shown buret

Calculates the actual FAS concentration

This FAS concentration is obtained from equivalence to the
dichrom

3. Discussion
3.1 Data and result
2.3. Data and Result
a. Experiment I (Preparation of Primary Standard Solution)

Num. Treatment Picture Observation


Prepare 25ml solution from
an accurately weighed
1. sample to 0.0002 g of
K2Cr2O7 to be analyzed.
The Pottasium dichromate is
transferred into a 100ml
volumetric flask and about
2.
75ml of deionised water is
added, rinsing out the beaker
glass
has been dried in the oven at
105C for 2 hour and kept in
desiccator
Using volumetric pipette
with a bulb on the top
Deionised water is added to
the volumetric flask up to the
mark.

The solute is dissolved by
swirling the flask, or by
3.
stoppering it and inverting it
repeatedly
25ml of the solution is
7. transferred into Erlenmeyer
flask by volumetric pipette
3-5 drops of concentrated
H2SO4 solution is added using
a volumetric pipette
8. Store it until the temperature
is cooled down. When the
flask is too warm, soak the
bottom of the flask with
water.
Swirled until all of the solute
has dissolved
The flask is labelled and set
to one side
Calculate the concentration
of Pottasium dichromate
solution as primary standard
solution
Note that beads of water have
formed on the flask walls
indicating that the flask is
still dirty. So ensure that it is
ready to use.
The H2SO4 is colorless,
odorless, extremely
corrosive, oily liquid. When
the concentrated acid mixes
with water, large amounts
of heat are released; enough
heat can be released at once
to boil the water and spatter
the acid
 2-3 drops of ferroin indicator The colour of solution turns
9. is added by using a drop to green
pipette. Swirled.

b. Experiment II (Determination of Secondary Standard Solution)

Num. Treatments Pictures Observation
3.92 g of Ferro Ammonium
Sulfat is accurately weighed
1.
out on an analytic balance
using a beaker glass
 10 mL of distilled water added
2. in a beaker glass, stir it until the The solution becomes clear
solute is dissolved

Carefully transfer weighed

chemical to funnel placed on a
100mL volumetric flask.
3. No changes
Wash beaker glass & funnel
with distilled water into flask
using wash bottle

Take 2 mL of concentrated
HCl solution using
volumetric pipette and put it
4.
into a 100 ml volumetric flask.
Dripping H2SO4 on the inside
neck of the flask.
Bring it up to volume (liquid
reaches the ring graduation
5.
line) by adding deionised
water
The mixture is shaken in the
6. volumetric flask until the
sample dissolves
The H2SO4 is colorless,
odorless, extremely
a corrosive, oily liquid. When
the concentrated acid mixes
with water, large amounts
of heat are released; enough
heat can be released at once
to boil the water and spatter
the acid
until the bottom of the
solution meniscus lines up
exactly with the volume mark
 [Titration]
Place the buret in a buret clamp
attached to a large ring stand.

Clean a buret by rinsing with The buret is clean enough

several portions (about 10 mL) when water droplets do not
7.
of tap water. This rinse water cling to the inner surface
can be poured down the drain.

Open the stopcock for a few

seconds to remove all air from
the tip.

Place the flask containing the

primary standard which is
Potassium Dichromate under
the buret to be titrated.
Using a funnel, fill the buret
8. with titrant (FAS) to a level
above the zero mark and clamp
the buret up vertically.
Add the titrant slowly from the
buret while swirling the
contents of the flask to assure
These respond to
characteristic changes in the
properties of solutions during
titration. The substance
which is added specially
(termed an indicator)
changes colour into red.
There is clouding or turbidity
in the solution because of the
formation of an insoluble
phase
 adequate mixing until the
indicator endpoint is reached.

When the end point has been

reached, allow the solution to
sit for 10 seconds so the liquid Read volume when solution
in the buret can settle, then turns red at end point.
9.
read the buret. Subtract the Calculate the molarity
initial buret reading from the
final reading to obtain the
volume of titrant used.

3.2 Discussion
The practicum was being held on Thursday, 26th of October 2017 at 08.30 AM until
11.00 AM. This time we were asked to do an experiment about Standardization Solutions.
The required equipments are calibrated burette, burette stand, Erlenmeyer flask or beaker,
volumetric flask, chemical balance, drop pipette, funnel, and stirring rod. While the
required chemicals are Pottasium dichromate (K2Cr2O7), Ferro Ammonium Sulfat atau
FAS (Fe(NH4)2(SO4)2.6H2O), strong H2SO4, ferroin indicator, aquadest.
Standardization is the process of determining the exact concentration (molarity) of a
solution. Titration is one type of analytical procedure often used in standardization. In a
titration, an exact volume of one substance is reacted with a known amount of another
substance. The point at which the reaction is complete in a titration is referred to as
the endpoint. A chemical substance known as an indicator is used to indicate (signal) the
endpoint. The indicator used in this experiment is ferroin. Ferroin, an organic compound,
is colorless in acidic solution and pink in basic solution.
To standardize an analytical method we use standards containing known amounts of
analyte. The accuracy of a standardization, therefore, depends on the quality of the
reagents and glassware used to prepare these standards. For example, in an acidbase
titration the stoichiometry of the acidbase reaction defines the relationship between the
moles of analyte and the moles of titrant. In turn, the moles of titrant is the product of the
titrants concentration and the volume of titrant needed to reach the equivalence point.
We divide analytical standards into two categories: primary standards and secondary
standards. A primary standard is a reagent for which we can dispense an accurately
known amount of analyte. For example, a 0,4903gr sample of K2Cr2O7 contains 16,67
104 moles of K2Cr2O7. If we place this sample in a 100mL volumetric flask and dilute to
volume, the concentration of the resulting solution is 1,7 103 M. A primary standard
must have a known stoichiometry, a known purity (or assay), and it must be stable during
long-term storage. Because of the difficulty in establishing the degree of hydration, even
after drying, a hydrated reagent usually is not a primary standard. Reagents that do not
meet these criteria are secondary standards. The concentration of a secondary standard
must be determined relative to a primary standard. So here are the process.
Measure the exact volume of standard solution required from buret readings before
and after the titration. Since the molarity of the standard solution is known, the number of
moles of titrant can be calculated. From a knowledge of the equation for the reaction, the
number of moles of constituent present in the sample can also be calculated. The most
accurate and convenient way of preparing a standard solution is to weigh the reagent,
dissolve it, and dilute the solution to a definite volume in a volumetric flask. This method
can only be used if the reagent is a primary standard. The solution is then standardized by
titrating it against a primary solution. This standardized solution is caled a secondary
standard.
Clean the buret before use and rinse with water. If any drops of water collect on the
walls, the buret is not clean. Once the buret is clean, rinse it with the aquades before filling
it. Pour about 5 mL of the aquades into the buret and, holding the buret almost
horizontally, rotate it slowly so that the titrant cleans the entire buret. Do this three times.
Place the buret in a buret clamp attached to a large ring stand. Using a funnel, fill the
buret with the titrant (FAS) to a level above the zero mark. Place the Erlenmeyer flask
containing K2Cr2O7 under the burret and open the stopcock for a few seconds to remove
all air from the tip and fill it. The top of the solution should now be below the zero mark.
Add the titrant slowly from the buret while swirling the contents of the flask to assure
adequate mixing. As the end point is approached, the titrant must be added very slowly -
a drop at a time. There is an indication as the end point is approached. If the end point is
a color change, the change is produced momentarily where the reagent drops into the
solution, but fades with stirring into the solution. This fading occurs more slowly as the
endpoint is approached.
In this experiment, the colour of the K2Cr2O7 solution turns to red after a few drops
of titrant (FAS) has been added. Stop the titration immediately when the end point has
been reached. Allow the solution to sit for 10 seconds so the liquid in the buret can settle,
then read the buret. Subtract the initial buret reading from the final reading to obtain the
 volume of titrant used. It is show that 7ml has been added. And because the titrat turns to
red at the end, means that the titrat contains acid.
Indicators are used to determine the end point of the titration. An indicator is used in
acid-base and oxidation-reduction titrations. The color change of the indicator should be
near the equivalence point of the reaction. Calculating process is shown below.
M (molar) = (1 (g)/ BM (g/mol)) / (volume (L))
V1 x N1 = V2 x N2
Where N2 and V2 represent normality and volume of stock solution and V1 equals volume
to which stock solution should be diluted to obtain desired normality, N1.

Calculation:
Reaction occurred :
K2Cr2O7 + 4 H2SO4 K2SO4 + Cr2(SO4)3 + 4 H2O +3 [O]
Redox reaction :
6 FeSO4 + 3 H2SO4 + 3 [O] 3 Fe2(SO4)3 + 3 H2O
K2Cr2O7 + 6 FeSO4 + 7 H2SO4 3 Fe2(SO4)3 + K2SO4 + Cr2(SO4)3 + 7 H2O
----------------------------------------------------------------------------------------------
(Cr2O7)2- + 6Fe2+ + 14H+ 6Fe3+ + 2Cr3+

1 M (Cr2O7)2- equivalent with 6 M Fe3+

So 1 M (Cr2O7)2- = 6 N
K2Cr2O7 which is being used is 0,4903 g, or 0.01 M = N1 = 0.06 N
V K2Cr2O7 = V1 = 25 mL
V Fe2+ = V2 = 7 mL
N Fe2+ = N2 (?)
V1N1 =V2N2 N2 can be calculated. M Fe2+ = N Fe2+
V1 . N1 = V2 . N2
25 . 0,06 = 7 N2
25 0,06
N2=
7
= 0,2142 N
The final result of concentrated standardize a solution is 0,2142 N,

4. Conclusion
3.1. Conclusion
In volumetric titrimetry one uses a standard solution the concentration of which is known
with great precision and which reacts stoichiometrically with the analyte. Standard
solutions are referred to either as primary standards or secondary standards. Primary
standards can be prepared by weighing directly and dissolving to a measured volume the
reagent which is to react with the analyte. But primary standards must meet stringent
requirements:
a. High purity
b. Stability in presence of air
 c. Absence of any water of hydration which might vary with changing humidity and
temperature.
d. Dissolves readily to produce stable solutions in solvent of choice
e. A larger rather than smaller molar mass

So as to be useful as a measure of the quantity of analyte in a sample, a standard solution

must meet four criteria:
a. The reagent in the solution must have sufficient stability so that its concentration need
be determined only once. Any deterioration in strength due to reaction with
components of water or air would make the reagent unacceptable.
b. The reagent in the solution must react rapidly with the analyte. Slow approaches to
equilibrium can cause erroneous judgments about reaction completeness.
c. The reaction of the analysis must occur with a completeness easily detectable by an
appropriate indicator.
d. The reagent must react with the analyte in a simple and stoichiometrically predictable
manner. Any side reactions would render a reagent unacceptable

Determination of the concentration of a standard solution.

The direct method of solution standardization is the obvious choice if the reagent is a
primary standard which meets all of the criteria described above and whose weight offers
a repeatable observation proportional to the number of moles of substance expected.
Solutions of Potassium Dichormate and FAS can be prepared in this manner. The method
of standardization can be used if a primary standard reacts quantitatively with the reagent
needed in the standard solution. The following two relationships will be useful:

Execution will include discussion of techniques of dilution and the use of the equation:

3.2. References
Asuero, Agustin G. Michalowski, Tadeusz. 2011. Comprehensive Formulation of
Titration Curves for Complex Acid-Base Systems and Its Analytical Implications.
Critical Reviews in Analytical Chemistry 41:2, pages 151-187
Dukhin, Andrei S. Goetz, Philip J. 2017. Characterization of Liquids, Dispersions,
Emulsions, and Porous Materials Using Ultrasound. Elsevier.
Granholm, Kim. Sokalski, Tomasz. Lewenstam, Andrzej. Ivaska, Ari. 2015. Ion-
selective electrodes in potentiometric titrations; a new method for processing and
evaluating titration data. Analytica Chimica Acta
Mndez, J Martin. GonzlezIsmael, P..Pez. 2017. Steady state equivalence in speciation:
Reaction networks in acidbase aqueous solutions. Chemical Engineering
Research and Design, Pages 132-140
 P.C. Thijssen. 2010. 8 The titration system. Elsevie

5. In-depth knowledge
1. Explain why the dilution experiment has to use volumetric flask? and why the inside neck
of volumetric flask has to be dried properly before adding the aquadest?
Because a volumetric flask calibrated to contain a precise volume at a particular
temperature, so it is used for precise dilutions and preparation of standard solutions. The
inside neck of volumetric flask has to be dried properly before adding the aquades because
grease or other contaminants may cause the water to bead on the inside surface of the flask.
We don't want any remaining reagents on the glass surface since they could react with the
solutions and change analysis results. Also if the glass is not perfectly clean, water will not
wet its surface, and it will be present on the glass surface in the form of droplets. Don't dry
the glass surface with towels, just leave it protected from the dust

2. Why titration has to be stopped when the colour of solution is changing?

Indicators, which change color to indicate when the reaction reached the end point. The
end point of a titration is when the reaction between the two solutions has stopped. Thats
why we should stop adding the titrant since the reactant within the solution of unknown
concentration has been completely neutralized.

3. What is equivalent and final points of titration in this experiment?. What is the effect of
the points on the analysis and solution standarisation?
The equivalence point is the exact point in a titration when moles of one titrant equal the
moles of the substance being titrated. The endpoint is the point where the system changes
when the moles of the reacting titrant exceed the moles of the substance being titrated. The
amount of titrant released from the buret at the endpoint signifies the volume of solution
necessary to complete the reaction. From this given volume, the concentration of either
titrant or analyte can be determined when equilibrium is reached between reactant and
product. Release the titrant into the analyte solution until the reaction has occurred
completely. This will become apparent when the solution remains a constant redcolor. Use
the calculated molarity from the volume of titrant to standardize the solution produced.

4. Verify the accuracy of both molaritas and normalitas equations in this experiment. Show
the complete reactions!
Reaction occurred :
K2Cr2O7 + 4 H2SO4 K2SO4 + Cr2(SO4)3 + 4 H2O +3 [O]
Redox reaction :
6 FeSO4 + 3 H2SO4 + 3 [O] 3 Fe2(SO4)3 + 3 H2O
K2Cr2O7 + 6 FeSO4 + 7 H2SO4 3 Fe2(SO4)3 + K2SO4 + Cr2(SO4)3 + 7 H2O
-----------------------------------------------------------------
(Cr2O7)2- + 6Fe2+ + 14H+ 6Fe3+ + 2Cr3+

1 M (Cr2O7)2- equivalent with 6 M Fe3+

So 1 M (Cr2O7)2- = 6 N
K2Cr2O7 which is being used is 0,4903 g, or 0.01 M = N1 = 0.06 N
V K2Cr2O7 = V1 = 25 mL
V Fe2+ = V2 = 7 mL
N Fe2+ = N2 (?)
V1N1 =V2N2 N2 can be calculated. M Fe2+ = N Fe2+
V1 . N1 = V2 . N2
25 . 0,06 = 7 N2
25 0,06
N2= 7
= 0,2142 N
The final result of concentrated standardize a solution is 0,2142 N,