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GENERAL

CHEMISTRY
LABORATORY
MANUAL
YILDIZ TECHNICAL UNIVERSITY
FACULTY OF ART & SCIENCE
CHEMISTRY DEPARTMENT

COURSE FOR: 1170-1160-1100


EDITED BY: Doç. Dr. Bahadır KESKİN

İSTANBUL- 2015
GENERAL CHEMISTRY
LABORATORY MANUAL
COURSE FOR: 1170-1160-1100

YILDIZ TECHNICAL UNIVERSITY


FACULTY OF ART & SCIENCE
DEPARTMENT OF CHEMISTRY

PREPARED BY

Inorganic Chemistry Division

EDITED BY: Doç. Dr. Bahadır KESKİN

ISTANBUL, 2015

i
NAME, SURNAME :
Photo
NUMBER:
TERM / GROUP NUMBER:
LECTURER:
SENIOR LECTURER:

EXP.
EXPERIMENT DATE SIGNATURE
NO.
Rate of Reactions:
1 …./… / 20…
Examination of the reaction rate

Gases:

2 Determination of The Molecular Weight …./… / 20…


of Volatile Liquids

3 Chemical Equilibrium …./… / 20…

pH Concept:

4 Determination of pH by Colorimetric …./… / 20…


Method

5 Acids and Bases …./… / 20…

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GENERAL CHEMISTRY

LABORATORY MANUAL

COURSE FOR: 1170-1160-1100

TABLE OF CONTENTS

TABLE OF CONTENTS ..................................................................................................... i

LABORATORY EQUIPMENTS ....................................................................................... ii

EXPERIMENT 1 Examination of the reaction rate……………………………………..15

EXPERIMENT 2 Gases…………………………………………………………………..10

EXPERIMENT 3 Chemical equilibrium……………………………………………….. 26

EXPERIMENT 4 pH Concept…………………………………………………………... 20

EXPERIMENT 5 Acid Base Titration…………………………………………………..26

APPENDIX………………………………………………………………………………….. 31

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LABORATORY EQUIPMENTS

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EXPERIMENT -1-

EXAMINATION OF THE REACTION RATE

PURPOSE
The purpose of this experiment is to determine the rate law and activation energy of a chemical
reaction.

THEORY
Chemical kinetics, also known as reaction kinetics, is the study of rates of chemical processes.
Chemical kinetics includes investigations of how different experimental conditions can influence
the speed of a chemical reaction and yield information about the reaction's mechanism and
transition states, as well as the construction of mathematical models that can describe the
characteristics of a chemical reaction.

Factors affecting reaction rate:


1. Nature of the reactants
Depending upon what substances are reacting, the time varies. Acid reactions, the formation of
salts, and ion exchange are fast reactions. When covalent bond formation takes place between
the molecules and when large molecules are formed, the reactions tend to be very slow. Nature
and strength of bonds in reactant molecules greatly influences the rate of its transformation into
products. The reactions which involve lesser bond rearrangement proceed faster than the
reactions which involve larger bond rearrangement.

2. Physical state
The physical state (solid, liquid, or gas) of a reactant is also an important factor of the rate of
change. When reactants are in the same phase, as in aqueous solution, thermal motion brings
them into contact. However, when they are in different phases, the reaction is limite to the
interface between the reactants. Reaction can only occur at their area of contact, in the case of a
liquid and a gas, at the surface of the liquid. Vigorous shaking and stirring may be needed to
bring the reaction to completion. This means that the more finely divided a solid or liquid
reactant, the greater its surface area per unit volume, and the more contact it makes with the
other reactant, thus the faster the reaction. To make an analogy, for example, when one starts a
fire, one uses wood chips and small branches—one doesn't start with large logs right away. In
organic chemistry, on water reactions are the exception to the rule that homogeneous reactions
take place faster than heterogeneous reactions.

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3. Concentration
Concentration plays a very important role in reactions according to the collision theory of
chemical reactions, because molecules must collide in order to react together. As the
concentration of the reactants increases, the frequency of the molecules colliding increases,
striking each other more frequently by being in closer contact at any given point in time.
Think of two reactants being in a closed container. All the molecules contained within are
colliding constantly. By increasing the amount of one or more of the reactants it causes these
collisions to happen more often, increasing the reaction rate.

4. Temperature
Temperature usually has a major effect on the rate of a chemical reaction. Molecules at a higher
temperature have more thermal energy. Although collision frequency is greater at higher
temperatures, this alone contributes only a very small proportion to the increase in rate of
reaction. Much more important is the fact that the proportion of reactant molecules with
sufficient energy to react (energy greater than activation energy: E > Ea) is significantly
higher and explained in detail by the Maxwell–Boltzmann distribution of molecular
energies.
The 'rule of thumb' that the rate of chemical reactions doubles for every 10°C temperature rise
is a common misconception. This may have been generalized from the special case of
biological systems, where the Q (temperature coefficient) is often between 1.5 and 2.5.
A reaction's kinetics can also be studied with a temperature jump approach. This involves using
a sharp rise in temperature and observing the relaxation rate of an equilibrium process.

Figure 1. Rate of Reactions

Catalysts
Generic potential energy diagram showing the effect of a catalyst in a hypothetical endothermic
chemical reaction. The presence of the catalyst opens a different reaction pathway (shown in
red) with lower activation energy. The final result and the overall thermodynamics are the same.

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A catalyst is a substance that accelerates the rate of a chemical reaction but remains chemically
unchanged afterwards. The catalyst increases rate reaction by providing a different reaction
mechanism to occur with lower activation energy.

Figure 2. Catalyst efect on rate of reaction.

CHEMICALS and EQUIPMENTS


Glass rod; 5 test tube; graduated cylinder; 2 beakers; 250 mL beaker; droppers; pipettes.
Solution A: 4 g KIO3 in a liter; B solution: 5 g starch in a liter; 4 mL concentrated H2SO4 and
1 g Na2SO4.

PART A. Effect of Concentration on Reaction Rate:


PROCEDURE
1. Take two dry test tubes, labeled A and B.
2. 5 ml of A solution and 5 ml of B solution transferred from two tubes.
3. Take 5 dry test tubes and transferred from 5 mL B solution of each tubes.
4. Transferred 5 mL B solution into graduated cylinder.
5. A and B at the same time the test solution is transferred to container. Stir with glass rod. Mix
until the blue color to save time.
6. Clean the container and dry it. In A concentration by changing the times you repeat this
process in 5(In graduated cylinder 1 mL water + 4 mL A solution).
7. Clean the container and dry it. In A concentration by changing the times you repeat this
process in 5(In graduated cylinder 2 mL water + 3 mL A solution).
8. Clean the container and dry it. In A concentration by changing the times you repeat this
process in 5(In graduated cylinder 3 mL water + 2 mL A solution).
9. Clean the container and dry it. In A concentration by changing the times you repeat this
process in 5(In graduated cylinder 4 mL water + 1 mL A solution).
10. Save the table 1 to calculate the concentrations of KIO3.
Note: Solution A: (4gr KIO3 /214)/ 1L = 0.02 mol/L = 0.02 mmol/mL

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PART B. Effect of Temperature on Reaction Rate:
PROCEDURE

1. Take 3 dry test tubes, and graduated cylinder.


2. Each three separate test tube is transferred to the 10 mL of A solution using graduated
cylinder.
3. Three separate test tube is transferred to the 10 mL of B solution.
4. A and B at the same time the test solution is transferred to container. Stir with glass rod. Mix
until the blue color to save time.
5. Put 100 mL water in 250 mL beaker for using water bath.
6. Put the all test tubes which contain A and B solutions in water bath. Measure the
temperature of water bath. It should be 15-20°C. Tubes in water bath for 5 minutes wait
before transferred to container. Stir with glass rod. Mix until the blue color to save time.
7. In 6 studies should be repeated in the three different temperatures. And save the time also.

Questions:
1. How can be established a correlation between concentration of substances reacting with the
reaction time?
2. How can be established a correlation between concentration of substances reacting with the
reaction rate?
3. Complete the Table 2?
4. Is the effect of temperature on reaction time?
5. A mix of 5 mL A and 5 mL B solutions will occur with the blue color of time what
happens in 10°C and 40°C?

Results:

Table 1: Effect of concentration on reaction rate


Reactants Total mL Concentration of Time until the blue
nitrate ions in A color seen in (sec)
solution
A mL Water mL B mL
5 0 5 10
4 1 5 10
3 2 5 10
2 3 5 10
1 4 5 10
Calculations:

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Table 2: The effect of temperature on reaction rate

o
Experiment Number Temperature C Time (sec)
1
2
3
4
5
6

Graphic:

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EXPERIMENT -2-

GASES:
DETERMINATION OF THE MOLECULAR WEIGHT OF
VOLATILE LIQUIDS

PURPOSE
The purpose of this experiment is to comprehend about the Gas Laws, the Dumas Method of
Molecular Weight determinations, and determination of chemical formulas.
EQUIPMENTS
Erlenmeyer flask (250 mL); a piece of aluminum foil; rubber band; beaker (600 mL);
hot plate.
CHEMICALS & OTHER MATERIALS
Water, conc. HCl, unknown liquid.
THEORY
In this experiment you will be using the Dumas Method for determining the molecular mass of a
volatile liquid. Volatile liquids are those, which have low boiling points. We will vaporize the
liquid in a flask to expel the air and replace it with vapor of the liquid. The vapor will then be
condensed by cooling, allowing the air to reenter. The difference in mass will be the quantity of
vapor that filled the entire volume of the flask at the elevated temperature and pressure.
Knowing the barometric pressure, the temperature and the volume of the vapor we should be
able to calculate the moles of vapor, n, using the ideal gas law:

PV = nRT
In this equation, P is the barometric pressure, V is the volume of the flask, R is the universal gas
constant (0.082 L.atm/mol.K), and T is the Kelvin temperature of the vapor.
For gases at moderate temperatures and pressures this Equation of State is rather simple. Known
as the Ideal Gas Law, this single equation incorporates the four Historical Gas Laws:
Historical Law Relationship Discovered

Boyle’s Law P ~ 1/V Charles’ Law V ~ T


Gay-Lusaac’s Law P ~ T
Avogadro’s Hypothesis V ~ n
In combination, these Laws give us: PV = nRT

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Historically, fifty years after Amedeo Avogadro enunciated his hypothesis that equal volumes of
a gas contain equal numbers of molecules (read moles) one of his students, Stanislao
Cannizzario, showed that this hypothesis could be used to determine the Molecular Weights
of gases. In modern terms, the number of moles of a gas can be determined from the easily
measurable parameters V, T and P via the above Ideal Gas Law:

n = PV / RT

If the mass (m) of the gas is also known, and this is also easily measurable, then we can
determine its Molecular Weight from:

MW = m/n

After the mass and moles of the vapor are known, the molecular mass can be determined by
dividing. The molecular mass can be compared to the following table to make a determination
of identity of the unknown.

Name of Substance Molecular Formula Molecular Mass

Acetone CH3COCH3 58.0 g/mol


Cyclohexane C6H12 84.0 g/mol
Ethanol CH3CH2OH 46.0 g/mol
Hexane C6H14 86.0 g/mol
Methanol CH3OH 32.0 g/mol
n-Pentane CH3CH2CH2CH2CH3 72.0 g/mol

PROCEDURE
1. Weigh a clean and dry 250 mL Erlenmeyer flask, a piece of aluminum foil, and a rubber
band to the nearest 0.001 g. flask, clamp, Pin, thermometer, balance
2. Fill a 600 mL beaker halfway with water. Heat it to boiling on a hot plate.
3. Add about 10 mL of an unknown liquid to the flask and cover it with the foil. Secure the foil
with the rubber band as a cover for the flask. Poke a small pinhole in the foil to allow a limited
exchange of gases with the room.
4. Submerge the flask into the hot water bath and clamp it in place. Put the flask as far into the
boiling water as you can without getting the foil wet. Measure the temperature of the hot water
bath.

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5. Watch the liquid level inside of the flask. The liquid will vaporize rather quickly. As soon as
the last bit of liquid inside the flask has vaporized, remove the flask from the boiling water. Dry
off the exterior of the flask, making sure not to disturb the foil covering. Allow the flask to cool
back to room temperature. Measure the boiling water temperature.
6. Measure the mass of the flask to the nearest 0.001 g.
7. Use a 100 mL graduated cylinder to determine the volume of the flask by filling the flask to
the rim with water.
8. Repeat the procedure if time allows with a second flask. Record this data as Trial 2 in your
data table.
9. Measure the barometric pressure in the room.
REPORTS FOR ASSIGNMENT
Data Table (Trial 1)
Mass of flask, foil, and rubber band g
Temperature of boiling water bath … oC …. K
Mass of the flask with condensed vapor g
Volume of flask mL
Barometric pressure in the room atm

Data Table (Trial 2)

Mass of flask, foil, and rubber band g


Temperature of boiling water bath ..… oC …. K
Mass of the flask with condensed vapor g
Volume of flask mL
Barometric pressure in the room atm

Calculations: (Place the answers to each calculation in the Calculations chart below)
1. Determine the number of moles of vapor that filled the flask using PV = nRT. Show all your
work!
2. Determine the mass of the vapor in the flask. Show all work!
3. Determine the formula mass of your unknown substance. Show all work!

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4. If a second trial was run follow the same sequence to determine its formula.
5. Make a guess as to the identity of your unknown form the information in the first table in the
introduction. If you did two trials use the average value to make your guess.
6. Ask your teacher for the identity to confirm your results. Calculate the percent error for your
experimental molecular mass.
Calculations Table
Trial 1 Trial 2

Moles of vapor mol mol


Mass of vapor g g
Formula mass of compound g/mol g/mol
Percent error % %
Formula mass of compound
Identity of unknown
g/mol
substance
Average formula mass g/mol

Average Percent error %

Questions:
1. If insufficient amount of liquid unknown had been used, how would this affect the value of
your experimental molecular mass? Explain.
2. Answer the following by indicating whether the final result would be higher or lower. Then
explain why.
a. How would your molecular mass be affected if all of the liquid were not vaporized when the
flask was removed from the water bath?
b. How would your molecular mass be affected if the flask were not dried before the final
weighing with the condensed vapor inside.
c. How would your molecular mass be affected if the flask were removed from the water bath
before the vapor had reached the temperature of the boiling water?
3. Near condensation temperatures, vapors are likely to be non-ideal. Would you expect such
behavior to make your molecular mass too high or too low? Explain.
4. What are the major sources of error in your determination of the molecular mass. Describe
how each source of error might have affected your results.

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5. Isobutyl alcohol would not be a good choice as a volatile liquid in this experiment. Explain.
Be specific. How would you modify the experiment so that it could be used?
6. Why is the mass of air in the flask NOT taken into account in this experiment?
7. The Molecular Weight of an unknown liquid is determined using the Dumas Method. The
following data has been obtained:
Atmospheric Pressure = 754.6 Torr
Vol. Flask = 213 mL
Temp. of Water Bath = 100oC
Mass of Re-Condensed Liquid = 0.582g
What is the Molecular Weight of the liquid?

Figure 3. The experimental apparatus of determining the molecular weight of a volatile liquid

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EXPERIMENT -3-

CHEMICAL EQUILIBRIUM

PURPOSE
The purpose of this experiment is to
1. study chemical equilibria.
2. investigate the effects of (a) changing concentrations and (b) changing temperature in
equilibrium reactions.
THEORY

Two important questions are asked about every chemical reaction: (a) How much product is
produced and (b) How fast is it produced? The first question involves chemical equilibrium and
the second question belongs to the domain of chemical kinetics. Some reactions are irreversible
and they go to completion (100% yield). When you ignite methane gas in your gas burner in the
presence of air (oxygen), methane burns completely and forms carbon dioxide and water.

CH4(g) + 202(g)  CO2(g) + 2H2O(g)

Other reactions do not go to completion. They are reversible. In such cases, the reaction can go
in either direction: forward or backward. For example, the reaction

Fe3+(aq) + SCN-(aq)  FeSCN2+(aq)

is often used to illustrate reversible reactions. This is so because it is easy to observe the
progress of the reaction visually. The yellow Fe3+ ion reacts with thiocyanate ion to form a deep
red complex ion, FeSCN2+. This is the forward reaction. At the same time, the complex red ion
also decomposes and forms the yellow iron(III) ion and thiocyanate ion. This is the backward
(reverse) reaction. At the beginning when we mix iron(III) ion and thiocyanate ion, the rate of
the forward reaction is at a maximum. As time goes on, this rate decreases because we have less
and less iron(III) and thiocyanate to react. On the other hand, the rate of the reverse reaction
(which began at zero) gradually increases. Eventually the two rates become equal. When this
point is reached, we call the process a dynamic equilibrium, or just equilibrium. When in
equilibrium at a particular temperature, a reaction mixture obeys the Law of Chemical
Equilibrium. This Law imposes a condition on the concentration of reactants and products
expressed in the equilibrium constant (K). For the above reaction between iron(lII) and
thiocyanate ions, the equilibrium constant can be written as

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K = [FeSCN2+]/[Fe3+][SCN-]
or in general
K = [products]/[reactants]

The brackets, [ ], indicate concentration, in moles/L, at equilibrium. As the name implies, the
equilibrium constant is a constant at a set temperature for a particular reaction. Its magnitude
tells if a reaction goes to completion or if it is far from completion (reversible reaction). A
number much smaller than 1 for K indicates that at equilibrium only a few molecules of products
are formed, meaning the mixture consists mainly of reactants. We say that the equilibrium lies
far to the left. On the other hand, a completion of a reaction (100% yield) would have a very
large number (infinite?) for the equilibrium constant. In this case, obviously the equilibrium lies
far to the right. The above reaction between iron(III) and thiocyanate has an equilibrium
constant of 207, indicating that the equilibrium lies to the right but does not go to completion.
Thus at equilibrium, both reactants and product are present, albeit the products far outnumber
the reactants.

The Law of Chemical Equilibrium is based on the constancy of the equilibrium constant. This
means that if one disturbs the equilibrium, for example by adding more reactant molecules, there
will be an increase in the number of product molecules in order to maintain the product/reactant
ratio unchanged and thus preserving the numerical value of the equilibrium constant. The Le
Chatelier Principle expresses this as follows: If an external stress is applied to a system in
equilibrium, the system reacts in such a way as to partially relieve the stress. In our present
experiment, we demonstrate the Le Chatelier Principle in two manners: (a) disturbing the
equilibrium by changing the concentration of a product or reactant; (b) changing the
temperature.

CHEMICALS and EQUIPMENTS


Solutions 0.1 M of ; KI NaHCO3 Dil. HCl
KCl (NH4)2C2O4 CH3COONa 0.2 M MgCl2
KSCN K2Cr2O7 NH4Cl 0.5 M NaOH
FeCl3 K2CrO4 Na2CO3 Test tubes
Hg(NO3)2 HNO3 NH3 Test tube holder
AgNO3
PROCEDURE

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PART A. Concentration Change and Chemical Equilibrium

1. Write the colors of the solutions of KCl, KSCN, FeCl3 ve Hg(NO3)2 to the Table 1.
2. Put a few drops of 0.1 M FeCl3 solution into the test tube and add the same amount of 0.1 M
KSCN and mix. Add water until you get clear, orange-red colored solution. Divide solution to
the 5 test tubes to be approximately the same amount of solution in each test tube.
3. Use the first tube as the color comparison standard and add 1 mL of solution of FeCl3 to the
second test tube. Add 1 or 2 g KCl to the third tube,. Add 1 mL of KSCN to the Fourth
numbered test tube and add 1 mL of Hg(NO3)2 to the fifth test. Mix each tube. Compare the
colors with the standard test tube. Write your observations in Table 2. Use the Table 1 data in
order to explain the the direction of the reaction
4. Add 5 mL diluted and 5 mL KI solution to the 1 mL FeCl3 solution. Brown colored I2 forms,
immediately.

2Fe3+ + I -  2Fe2+ + I2

Add over plenty amount of (NH4)2C2O4 solution, color disappears again. Oxalate ion, C2O42-,
gives stable Fe[C2O4] 3- complex with Fe3+. Write the reason of the disappearance of the color
of the I2 to the Table 3.
5. Experiment solutions are K2Cr2O7 and K2CrO4. Write the colors of the ions of Cr 2O72- and
CrO42- to the Table 4.
6. Put 5 ml 0.5 M K2Cr2O7 to a test tube. Add 0.5 M NaOH until the color change. Record your
observations to the Table 5.
7. Put 5 mL 0.5 M K2CrO4 to a test tube. Add HNO3 until color change.
8. Add 2 ml CaCl2 to the 5 mL K2Cr2O7solution. Record your observations to the Table 5.

PART B. Temperature and Chemical Equilibrium

Put 0.5 g NaHCO3 into a test tube, add 9-10 mL water, and divide the solution to 2 test tubes.
There exists the equilibrium of 2HCO3 - CO2 + CO32- + H2O.
This equilibrium shifts to right as the temperature increase. Boil and then cool one of the test
tubes for a while. Put CaCl2 solutions both of the test tubes. Which test tube consists of a white
precipitate more, why? (CaCO3 precipitates in water, Ca(HCO3)2 do not precipitates in water).
1. Put 1 mL AgNO3 to each one of 4 test tube, and add each of them 1 M 1 mL CH 3COONa.
2. Add 20 mL of water to the CH3COOAg precipitation consisting 1st tube. Write your
observations to Table 6.

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3. Add dil. HNO3 to the CH3COOAg precipitation consisting 2nd tube until a change occurs.
Write your observations to Table 6.
4. Add aqueous NH3 to the CH3COOAg consisting 3rd tube until a change occurs. Write your
observations to Table 6.
5. Add 2 mL 0.1 M KI solution to the CH3COOAg consisting 4th tube. Write your
observations to Table 6.
6. Put 1 mL Na2CO3 to test tube and add 1 mL of dil. CaCl2. Add over slowly dil. HCl and
write your observations to Table 6.
7. Put 2 mL 0.2 M MgCl2 to test tube, and add NH3 – H2O until a change occurs. Add over
slowly solid NH4Cl and mix until another change occurs. Write your observations to Table 6.

EVALUATION OF THE RESULTS

Table 1.
Ion or molecule Color

K+
Cl -
SCN -
Fe 3+

Fe(SCN)+

FeCl4 2-
Yellowish

Table 2.

Chemicals added to
Color change Reaction direction Reason of shift
equilibrium mixture
Fe3 from FeCl3+
Cl - from KCl

SCN - from KSCN

Reactions:

Table 3.

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Addition to equilibrium Color change Reaction direction Reason of shift
mix.

C2O42- from (NH4)2C2O4

Table 4.

Ion Color

Cr2O72-

CrO42-

Table 5. H+ concentration change effect to equilibrium system.

Cr2O72- + H2O  2CrO42- + H+

Original solution Added chemical to the Observation Explanation of the change


original solution

Cr2O72- OH- from NaOH

CrO42- H+ from HNO3

Cr2O72- Ba2+ from BaCl2

Reactions:

Questions:

1. For the reaction PCl3(g) + Cl2(g)  PCl5(g) at 25°C the equilibrium concentrations were as
follows: [PCl3] = 7.2 M, [PCl5] = 0.050 M, and [Cl2] = 7.2 M. Calculate the equilibrium constant
for the reaction.

2. The above reaction is exothermic. If the reaction was run at 15°C, would the equilibrium
concentration of [PCl5] be greater, the same, or smaller than 0.050 M?
If the reaction between iron (III) and thiocyanate ions yielded an equilibrium concentration of
0.2 M for each of these ions, what would be the equilibrium concentration of the red iron-
thiocyanate complex?

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EXPERIMENT -4-
pH CONCEPT:
EXAMINATION OF THE REACTION RATE

PURPOSE

The purpose of this experiment is to

1. To learn how to measure pH of a solution.

2. To understand the operation of buffer systems.

THEORY

We frequently encounter acids and bases in our daily life. Fruits, such as oranges, apples, etc.,
contain acids. Household ammonia, a cleaning agent, and Liquid Plumber are bases. Acids are
compounds that can donate a proton (hydrogen ion). Bases are compounds that can accept a
proton. This classification system was proposed simultaneously by Johannes Bronsted and
Thomas Lowry in 1923, and it is known as the Bronsted-Lowry theory. Thus any proton donor is
an acid, and a proton acceptor is a base. When HCl reacts with water

HCl + H2O  H3O+ + Cl-

HCl is an acid and H2O is a base because HCl donated a proton thereby becoming Cl-, and
water accepted a proton thereby becoming H3O+.

In the reverse reaction (from right to left) the H 3O+ is an acid and Cl-is a base. As the arrow
indicates, the equilibrium in this reaction lies far to the right. That is, out of every 1000 HCl
molecules dissolved in water, 990 are converted to Cl- and only 10 remain in the form of HCl at
equilibrium. But H3O+ (hydronium ion) is also an acid and can donate a proton to the base, Cl-.
Why do hydronium ions not give up protons to Cl- with equal ease and form more HCl? This is
because different acids and bases have different strengths. HCl is a stronger acid than hydronium
ion, and water is a stronger base than Cl-.

In the Bronsted-Lowry theory, every acid-base reaction creates its conjugate acid-base pair. In
the above reaction HCl is an acid which, after giving up a proton, becomes a conjugate base, Cl -.
Similarly, water is a base which, after accepting a proton, becomes a conjugate acid, the
hydronium ion.

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Conjugate base-acid pair

HCl + H2O  H3O+ + Cl-

Conjugate acid-base pair

Some acids can give up only one proton. These are monoprotic acids. Examples are
HCl, HNO3, HCOOH, and CH3COOH. The hydrogens circled are the ones donated. Other acids
yield two or three protons. These are called diprotic or triprotic acids. Examples are H2SO4,
H2CO3, and H3PO4. However, in the Bronsted-Lowry theory, each acid is considered
monoprotic, and a diprotic acid (such as carbonic acid) donates its protons in two distinct steps:

1. H2CO3 + H2O  H3O+ + HCO3-

2. HCO3- + H2O  H3O+ + CO32-

Thus the compound HCO3+ is a conjugate base in the first reaction and an acid in the second
reaction. A compound that can act either as an acid or a base is called amphiprotic. In the self-
ionization reaction

H2O + H2O  H3O+ + OH-

one water acts as an acid (proton donor) and the other as a base (proton acceptor). In pure water,
the equilibrium lies far to the left, that is, only very few hydronium and hydroxyl ions are
formed. In fact, only 1x10-7 moles of hydronium ion and 1x10-7 moles of hydroxide ion are
found in one liter of water. The dissociation constant for the self-ionization of water is

 H3O+  OH - 
Kd = 
 H 2O
2

This can be rewritten as

K w =  K d  H 2O  =  H3O +  OH - 
2

Kw, the ion product of water, is still a constant because very few water molecules reacted to
yield hydronium and hydroxide ions; hence the concentration of water essentially remained
constant. At room temperature, the Kw has the value of

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Yildiz Technical University, Faculty of Arts & Science, Deparment of Chemisty


K w =1x10-14 = 1x10-7  1x10-7 

This value of the ion product of water applies not only to pure water but to any aqueous (water)
solution. This is very convenient because if we know the concentration of the hydronium ion, we
automatically know the concentration of the hydroxide ion and vice versa. For example, if in a
0.01 M HCl solution HCl dissociates completely, the hydronium ion concentration is [H 3O+] –
1x10-2 M. This means that the [OH-] is

OH-  =K w / H3O+  =1x10-14 /1x10-2 =1x10-12 M

To measure the strength of an aqueous acidic or basic solution, P. L. Sorensen introduced the pH
scale.

pH= -log[H3O+ ]

In pure water, we have seen that the hydronium ion concentration is 1x10-7 M. The logarithm of
this is -7 and, thus, the pH of pure water is 7. Since water is an amphiprotic compound, pH 7
means a neutral solution. On the other hand, in a 0.01 M HCl solution (dissociating completely),
we have [H3O+] =1x10-2 M. Thus its pH is 2. The pH scale shows that acidic solutions have a pH
less than 7 and basic solutions have a pH greater than 7.

pH 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
acidic neutral basic

The pH of a solution can be measured conveniently by special instruments called pH meters. All
that must be done is to insert the electrodes of the pH meter into the solution to be measured and
read the pH from a scale. pH of a solution can also be obtained, although less precisely, by using
a pH indicator paper. The paper is impregnated with organic compounds that change their color
at different pH values. The color shown by the paper is then compared with a color chart
provided by the manufacturer.

There are certain solutions that resist a change in the pH even when we add to them acids or
bases. Such systems are called buffers. A mixture of a weak acid and its conjugate base usually
forms a good buffer system. An example is carbonic acid, which is the most important buffer in
our blood and maintains it close to pH 7.4. Buffers resist large changes in pH because of the Le
Chatelier principle governing equilibrium conditions. In the carbonic acid-bicarbonate (weak
acid-conjugate base) buffer system,

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Yildiz Technical University, Faculty of Arts & Science, Deparment of Chemisty


H2CO3 + H2O  HCO3- + H3O+

any addition of an acid, H3O+, will shift the equilibrium to the left. Thus this reduces the
hydronium ion concentration, returning it to the initial value so that it stays constant; hence the
change in pH is small. If a base, OH-, is added to such a buffer system, it will react with the
H3O+ of the buffer. But the equilibrium then shifts to the right, replacing the reacted hydronium
ions, hence again, the change in pH is small.

Buffers stabilize a solution at a certain pH. This depends on the nature of the buffer and its
concentration. For example, the carbonic acid-bicarbonate system has a pH of 6.37 when the two
ingredients are at equimolar concentration. A change in the concentration of the carbonic acid
relative to its conjugate base can shift the pH of the buffer. The Henderson-Hasselbalch equation
below gives the relationship between pH and concentration.
 A - 
pH=pK a +
 HA
In this equation the pKa is the -logKa, where Ka is the dissociation constant of carbonic acid
 HCO3-   H3O+ 
Ka =
 H 2CO3 
[HA] is the concentration of the acid and [A-] is the concentration of the conjugate base. The
pKa of the carbonic acid–bicarbonate system is 6.37. When equimolar conditions exist, then
[HA]=[A-]. In this case, the second term in the Henderson-Hasselbalch equation is zero. This is
so because [A-]/[HA]=1, and the log 1=0. Thus at equimolar concentration of the acid–conjugate
base, the pH of the buffer equals the pKa; in the carbonic acid–bicarbonate system this is 6.37.
If, however, we have ten times more bicarbonate than carbonic acid, [A -]/[HA]= 10, then log
10=1 and the pH of the buffer will be

pH = pKa + log [A-]/[HA] =6.37 + 1.0 =7.37

This is what happens in our blood-the bicarbonate concentration is ten times that of the carbonic
acid and this keeps our blood at a pH of 7.4. Any large change in the pH of our blood may be
fatal (acidosis or alkalosis). Other buffer systems work the same way. For example, the second
buffer system in our blood is

H2PO4 + H2O  HPO42- + H3O+

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Yildiz Technical University, Faculty of Arts & Science, Deparment of Chemisty


The pKa of this buffer system is 7.21. It requires a 1.6 to 1.0 molar ratio of HPO 42- to H2PO4-
to maintain our blood at pH 7.4.

CHEMICALS and EQUIPMENTS


pH: 2 -12 solutions 0.1 M NH4Cl
Methyl Orange 0.1 M NH3
Methyl Red Test tube
Bromothymol Blue Pipette
Alizarin Yellow

PROCEDURE
1. Put approximately 3 mL of pH 2, 3, 4, 5, 6 solutions into 5 different test tubes, respectively.
Add 2 drops of methyl orange indicator to each tube and mix. Observe and record the color
changes.
2. Repeat the same procedure for methyl red indicator for pH 3, 4, 5, 6, 7 solutions,
Bromothymol blue for pH 5, 6, 7, 8, 9 solutions, alizarin yellow for pH 9, 10, 11, 12, 13
solutions.
3. Record every indicators color observance pH range to the Table 1.
4. Put 3 mL NH4Cl into each one of 5 different test tubes. Add different indicator each of these
test tubes. Find the approximate pH of NH4Cl by means of color changes.

NH4Cl  NH4+ + Cl-

NH4+ + H2O  NH3 + H3O+ [H+] = [NH3]

5. Repeat the same trial with 0.1 M NH3 solution. Aproximate pH of the solution is estimated
and recorded to Table 2.

NH3 + H2O  NH4+ + OH-

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Yildiz Technical University, Faculty of Arts & Science, Deparment of Chemisty


EVALUATION OF THE RESULTS

Table 1.

Indicators pH

2 3 4 5 6 7 8 9 10 11 12 13

Methyl Orange

Methyl Red

Bromothymol Bue

Phenolphthalein

Alizarin yellow

Table 2.

Indicators Methy Methyl Bromothymol Phenolpht Alizarin pH


Comp. Orange Red blue halein yellow value

NH4Cl

NH3

Questions:

1. Phosphoric acid, H3PO4, is a triprotic acid. Show the formula of the conjugate base after two
protons have been donated.
2. The pKa of formic acid is 3.75. What is the pH of a buffer in which formic acid and sodium
formate have equimolar concentration? What is the pH of a solution in which the sodium
formate is 10 M and the formic acid is 1 M?
3. The pH of normal blood is 7.4. A diabetic patient’s blood gave a pH reading of 6.4. How
much more hydronium ion (H3O+ is in the blood of the diabetic patient?

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Yildiz Technical University, Faculty of Arts & Science, Deparment of Chemisty


EXPERIMENT -5-

ACID BASE TITRATION


PURPOSE

The purpose of this experiment is to

1. learn the techniques of titration

2. to determine the concentration of the concentration of acid.

THEORY

In order to measure how much acid or base is present in a solution we often use a method called
titration. If a solution is acidic, titration consists of adding base to it until all the acid is
neutralized. To do this, we need two things: (1) a means of measuring how much base is added
and (2) a means of telling just when the acid is completely neutralized.

How much base is added requires the knowledge of the number of equivalents of the base. The
number of equivalents is the product of the volume of the base added and the normality of the
base.

Equivalents = V x N

The titration is completed when the number of equivalents of acid equals the number of
equivalents of base.

Equivalents acid = Equivalents base

or

This is called the titration equation.


We use an indicator to tell us when the titration is completed. Indicators are organic compounds
that change color when there is a change in the pH of the solution. The end point of the titration
is when a sudden change in the pH of the solution occurs. Therefore, we can tell the completion
of the titration when we observe a change in the color of our solution to which a few drops of
indicator has been added.
Commercial vinegar contains 5-6% acetic acid. Acetic acid, CH3COOH, is a monoprotic acid.
Therefore, its concentration expressed in molarity or normality is the same. It is a weak acid and
when titrated with a strong base such as NaOH, upon completion of the titration, there is a

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Yildiz Technical University, Faculty of Arts & Science, Deparment of Chemisty


sudden change in the pH in the range from 6.0 to 9.0. The best way to monitor such a change is
to use the indicator phenolphthalein, which changes from colorless to a pink hue at pH 8.0-9.0.
Household vinegar is a 4 to 5 percent (by mass) acetic acid, CH 3COOH, solution. Generally,
caramel flavoring and coloring are also added to make the product sell better.
The percent by mass of acetic acid in vinegar is determined by titration, a measured mass of
vinegar to a phenolphthalein end point with a measured volume of the standardized sodium
hydroxide solution. The moles of acetic acid are calculated from the balanced equation

CH3COOH(aq) + NaOH(aq)  CH3COO-Na+ (aq) + H2O

Since the volume and molarity of the standardized NaOH solution are known, the moles of
NaOH used for the analysis are also known.
At the equivalence point in the titration, the number of moles of NaOH equals the number of
moles of CH3COOH. The mass of CH3COOH in the vinegar is determined by the following
equations.

M CH3COOH x V CH3COOH = M NaOH xV NaOH


mol CH3COOH= M NaOH x V NaOH
MW CH 3 COOH
grams of CH3COOH = mol CH3COOH x
mol CH 3COOH

Finally the precent by mass of CH3COOH in vinegar is calculated


grams of CH 3 COOH
x 100  % by mass of CH 3 COOH
grams of vinegar

Titration set up was given in the figure.

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Yildiz Technical University, Faculty of Arts & Science, Deparment of Chemisty


TITRANT

INDICATOR AND
ANALYTE
SOLUTION
Figure 4. Experimental set-up for the titration procedure

CHEMICALS and EQUIPMENTS


Oxalic acid Spatula
NaOH Erlenmeyer Flask
Phenolphthalein Graduated Cylinder
CH3COOH Pipette
Fruit Juica Stand
Distilled Water Burette

PROCEDURE

Standardization of 0.1 N NaOH solution

Weight 0.5 g oxalic acid dehydrates (H2C2O4.2H2O) and put it into a 250 mL Erlenmeyer flask.
Add 30-40 mL distilled water and mix. Add 2 drops of phenolphthalein. Rinse a clean burette
with 0.1 N NaOH solutions. Fill the burette until to zero line meniscuses. Titrate acid solution in
the flask with NaOH solution in the burette, slowly. When the pink color is observed, continue
the titration more slowly. The end point is the point where the pink color observed after the
addition of last drop of base. Read the volume of consumed NaOH solution amount from the
burette. The experiment is repeated for two times and factor is determined by using the

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Yildiz Technical University, Faculty of Arts & Science, Deparment of Chemisty


E.N.F.S
T=
1000
formula and the real normality of the base is calculated (Table 1.)

T = Weight

E= Equivalence weight

F= Factor

S= Consumption

Vinegar Analysis:

Put 5 mL of white vinegar into a 250 mL of erlenmeyer flask. Add 2 drops of phenolphthalein.
Titrate with the standardized NaOH solution. Continue to titration until light pink color
observed. Read the consumed base volume from burette and calculate the % CH 3COOH amount
of vinegar (Table 2.)

EVALUATION OF THE RESULTS


Table 1.
I. Trial II. Trial
Acid amount (g)
Equivalence weight of acid
Used acid equivalent gram
Consumed base amount (mL)
Used base equivalent gram
Normality of base
Avarage Normality

Calculations

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Yildiz Technical University, Faculty of Arts & Science, Deparment of Chemisty


Table 2.

I. Trial II. Trial


Normality of base
Consumed base amount (mL)
Used base equivalent gram
Equivalent gram of CH3COOH
Gram of CH3COOH in Sample
Equivalent CH3COOH gram in sample
Sample vinegar volume (mL)
Density of vinegar (g/mL)
Sample vinegar weight (g)
%(w:w) CH3COOH in vinegar
Average Normality

Vinegar Calculations

Questions:

1. After dissolved 3 g of oxalix acid (H2C2O4.2H2O) in 100 mL water, 30 mL of this solution is


titrated with NaOH. As the 25 mL of NaOH is used during the titration, what is the normality of
solution?
2. What is the normality and molatiry of 50 mL H2SO4 which is completely neutralized with
the 37.52 mL 0.1492 N NaOH solution?
3. What is the normality of 2.5 M HCOOH?
4. How many equivalents of sulfuric acid are in 20 mL of 0.35 N H2SO4 solutions? How many
grams?
5. What is the normality of an unknown acid if 35 mL of the acid can be titrated to an end point
by 15 mL of 0.25 N NaOH?

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Yildiz Technical University, Faculty of Arts & Science, Deparment of Chemisty


APPENDIX

Apendix 1. Table of Common Acid-Base Indicators

Indicator pH Range Quantity per 10 ml Acid Base


Thymol Blue 1.2-2.8 1-2 drops 0.1% soln. in aq. red yellow
Pentamethoxy red 1.2-2.3 1 drop 0.1% soln. in 70% alc. red-violet colorless

Tropeolin OO 1.3-3.2 1 drop 1% aq. soln. red yellow


2,4-Dinitrophenol 2.4-4.0 1-2 drops 0.1% soln. in 50% colorless yellow
alc.
Methyl yellow 2.9-4.0 1 drop 0.1% soln. in 90% alc. red yellow
Methyl orange 3.1-4.4 1 drop 0.1% aq. soln. red orange
Bromphenol blue 3.0-4.6 1 drop 0.1% aq. soln. yellow blue-
violet
Tetrabromphenol blue 3.0-4.6 1 drop 0.1% aq. soln. yellow blue
Alizarin sodium 3.7-5.2 1 drop 0.1% aq. soln. yellow violet
sulfonate
α-Naphthyl red 3.7-5.0 1 drop 0.1% soln. in 70% alc. red yellow
p-Ethoxychrysoidine 3.5-5.5 1 drop 0.1% aq. soln. red yellow
Bromcresol green 4.0-5.6 1 drop 0.1% aq. soln. yellow blue
Methyl red 4.4-6.2 1 drop 0.1% aq. soln. red yellow
Bromcresol purple 5.2-6.8 1 drop 0.1% aq. soln. yellow purple
Chlorphenol red 5.4-6.8 1 drop 0.1% aq. soln. yellow red
Bromphenol blue 6.2-7.6 1 drop 0.1% aq. soln. yellow blue
p-Nitrophenol 5.0-7.0 1-5 drops 0.1% aq. soln. colorless yellow
Phenol red 6.4-8.0 1 drop 0.1% aq. soln. yellow red
Neutral red 6.8-8.0 1 drop 0.1% soln. in 70% alc. red yellow
Cresol red 7.2-8.8 1 drop 0.1% aq. soln. yellow red
α-Naphtholphthalein 7.3-8.7 1-5 drops 0.1% soln. in 70% rose green
alc.
Thymol blue 8.0-9.6 1-5 drops 0.1% aq. soln. yellow blue
Phenolphthalein 8.0-10.0 1-5 drops 0.1% soln. in 70% colorless red
alc.
α-Naphtholbenzein 9.0-11.0 1-5 drops 0.1% soln. in 90% yellow blue
alc.
Thymolphthalein 9.4-10.6 1 drop 0.1% soln. in 90% alc. colorless blue
Nile blue 10.1-11.1 1 drop 0.1% aq. soln. blue red
Alizarin yellow 10.0-12.0 1 drop 0.1% aq. soln. yellow lilac

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Yildiz Technical University, Faculty of Arts & Science, Deparment of Chemisty


Appendix 2. Vapor Pressure of Water

Temperature Pressure Temperature Pressure Temperature Pressure


(degrees 0C) (mmHg) (degrees 0C) (mmHg) (degrees 0C) (mmHg)
0 4.6 34 39.9 68 214.2
1 4.9 35 42.2 69 223.7
2 5.3 36 44.6 70 233.7
3 5.7 37 47.1 71 243.9
4 6.1 38 49.7 72 254.6
5 6.5 39 52.4 73 265.7
6 7.0 40 55.3 74 277.2
7 7.5 41 58.3 75 289.1
8 8.0 42 61.5 76 301.4
9 8.6 43 64.8 77 314.1
10 9.2 44 68.3 78 327.3
11 9.8 45 71.9 79 341
12 10.5 46 75.7 80 355.1
13 11.2 47 79.6 81 369.7
14 12.0 48 83.7 82 384.9
15 12.8 49 88 83 400.6
16 13.6 50 92.5 84 416.8
17 14.5 51 97.2 85 433.6
18 15.5 52 102.1 86 450.9
19 16.5 53 107.2 87 468.7
20 17.5 54 112.5 88 487.1
21 18.7 55 118 89 506.1
22 19.8 56 123.8 90 525.8
23 21.1 57 129.8 91 546
24 22.4 58 136.1 92 567
25 23.8 59 142.6 93 588.6
26 25.2 60 149.4 94 610.9
27 26.7 61 156.4 95 633.9
28 28.3 62 163.8 96 657.6
29 30 63 171.4 97 682.1
30 31.8 64 179.3 98 707.3
31 33.7 65 187.5 99 733.2
32 35.7 66 196.1 100 760
33 37.7 67 205

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Yildiz Technical University, Faculty of Arts & Science, Deparment of Chemisty


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Yildiz Technical University, Faculty of Arts & Science, Deparment of Chemisty

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