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Institute of Chemistry
College of Science
University of the Philippines, Diliman, Quezon City
CHEMISTRY 26.1
Introduction to Quantitative Chemical Analysis
LABORATORY MANUAL
2017 EDITION
Chemistry 26.1: Introduction to Quantitative Chemical Analysis Laboratory Manual
(2017 Edition)
Institute of Chemistry, University of the Philippines Diliman ii
Foreword
This laboratory manual is intended for use in Analytical Chemistry Laboratory taken
by non-Chemistry major students. This manual was developed, researched and revised
by the Analytical Chemistry Academic Group of the Institute of Chemistry. The main
objective in this revised edition is to provide students with the best practical
procedures for learning chemistry by incorporating and amplifying features that
enhance their understanding of basic analytical techniques used in chemical
measurements. In addition, this manual was also developed to provide guidance in
the area of general laboratory safety. It is a part of our overall effort to
establish basic, safe operating practices so that students and teachers can do
effective teaching and research programs in a safe and healthy environment.
I would like to acknowledge the people that have made considerable contributions to
the completion of this current edition of Chemistry 26.1 laboratory manual.
Dr. Flerida A. Cariño
Director, Institute of Chemistry
(2017 Edition)
Institute of Chemistry, University of the Philippines Diliman iii
Acknowledgement
Following the 2009 and 2013 revision, the Analytical Chemistry Academic Group has
produced this third version of the new laboratory manual, set to be released in
2017, for the use of students of the University of the Philippines Diliman enrolled
in Chemistry 26.1: Analytical Chemistry Laboratory.
The 2017 edition adapts most of the content and revisions from the 2013 edition.
What differentiates this 2017 edition from the previous ones are as follows: (1)
modified procedures for most experiments, following microscaling and waste disposal
considerations, and (2) modified data sheets, both student’s and instructor’s
copies, for most experiments.
This 2017 version is a collective effort of the following instructors who patiently
reviewed and revised the experiments and details of the laboratory manual: Ms.
Rosemarie Elloisa Acero, Ms. Joyce Lyn Garcia and Mr. Cris Angelo Pagtalunan.
The cover of the 2017 edition is by Rajelle Hernandez, a BS Chemistry graduate of
UP Diliman.
(2017 Edition)
Institute of Chemistry, University of the Philippines Diliman iv
Contents
Students’
Guide .............................................................................
.................................................................... 1
Application of Statistical Concepts in the Determination of Weight Variation in
Samples ................... 8
Solution
Preparation .......................................................................
................................................................ 11
Iodine Clock
Reaction ..........................................................................
........................................................... 14
Common Ion Effect and
Buffers ...........................................................................
......................................... 17
Determination of the Solubility Product Constant of Calcium
Hydroxide ............................................ 21
Quantitative Determination of Soda Ash Composition by Double Indicator
Titration ....................... 24
Quantitative Determination of Total Hardness in Drinking Water by Complexometric
EDTA
Titration .........................................................................
...................................................................................
28
Quantitative Determination of Dissolved Oxygen Content by Winkler Redox
Titration .................... 31
Determination of Electrode
Potentials ........................................................................
................................. 34
Quantitative Determination of the Purity and Dissociation Constant of Potassium
Hydrogen Phthalate by Potentiometric
Titration .........................................................................
................................. 39
Quantitative Determination of Copper(II) Concentration by
Spectrophotometry ................................ 43
Quantitative Determination of Total Ion Concentration by Ion Exchange
Chromatography ............. 45
Laboratory Guidelines and Techniques in Analytical
Chemistry............................................................ 47
Instructions on Proper Use of
Instruments .......................................................................
.......................... 50
Preparation of Buffer
Solutions .........................................................................
............................................ 54
Properties of Common Acids, Bases, and Primary
Standards ................................................................. 56
Tolerances of Common Laboratory Glassware and
Equipment .............................................................. 57
Significant Figures and Error
Propagation .......................................................................
........................... 58
Periodic Table of
Elements ..........................................................................
.................................................. 60
(2017 Edition)
Institute of Chemistry, University of the Philippines Diliman 1
Students’ Guide
Pre-Laboratory Discussion
The instructor will give a pre-laboratory discussion for each experiment. This is
composed of a short introduction on the type of analysis to be performed and the
procedures of the experiment.
Post-Laboratory Discussion
After each experiment has been performed, the instructor will give a post-
laboratory discussion. This is composed of a detailed discussion of the concepts,
results of the experiment and possible sources of error, as well as proper
calculations and solutions.
Laboratory Performance
The laboratory performance of the student is evaluated for every experiment based
on the standards set by the instructor. The student is evaluated through attendance
during experiment day and through the laboratory procedures and techniques s/he
performs during the experiment.
Laboratory Group
Each student will work on each experiment with a partner or groupmates (in case of
odd-numbered classes).
Locker
Each pair or group will be assigned a locker, which should be kept clean and secure
at all times. The locker should also be lined with newspaper, manila paper or any
wrapper to avoid moisture accumulation and spillage. The contents of each locker
will be checked-out during the start of the semester and will be checked-in at the
last day of classes, to account for any loss which might have occurred during the
semester.
Data Notebook
The data notebook is required for each student. It should be an 8.5” x 11” bound
notebook with 50-60 leaves. All the right-hand pages of the notebooks should be
numbered at the upper right hand corner. The left-hand pages only serve as scratch
and area for note-taking. The first page/s of the notebook will serve as the table
of contents, which should be updated regularly. This page should have the following
format:
Figure SG-1. The format of the table of contents of the laboratory notebook.
Each student is required to submit a pre-laboratory report for each experiment a
day prior the actual experiment. This report includes the following: (a) the
OBJECTIVES of the experiment, (b) a LIST OF ALL GLASSWARE, MATERIALS, EQUIPMENT AND
REAGENTS (quantity included) to be used in the experiment, (c) SCHEMATIC DIAGRAM OF
THE PROCEDURE, (d) DIAGRAM/S OF SPECIAL SETUP/S, (e) WASTE DISPOSAL procedures and
(f) CALCULATIONS for solution preparation.
The data notebook will serve as the student’s guide during the experiment since all
laboratory manuals will not be allowed to be open inside the laboratory. The
calculations for solution preparation should include the volume of solution
required for dilution, concentration of a solution, mass of substances to be
weighed, etc. for all solutions to be prepared.
(2017 Edition)
Personal Protective Equipment (PPE)
Each student must wear the prescribed personal protective equipment (PPE), which
consists of the laboratory gown, goggles, long pants, and closed shoes (doll shoes
are NOT considered as closed shoes), before performing an experiment. A student
without complete PPE is considered absent for that particular experiment.
Materials and Other Requirements
Individual
laboratory manual
(1) laboratory notebook (50 sheets only, lesson plan style, covered with class
color and plastic)
laboratory gown
safety goggles
(2) bluebooks
(1) aspirator
Pair
wash bottle
liquid detergent (in PET bottle, diluted)
(5) pasteur pipettes
masking tape/sticker label
(5) spatulas
(2) tissue paper rolls
(2) round rags
(1) filter paper (whole)
permanent marker
Attendance
A student is considered late if s/he comes to class 15-30 minutes after the class
has started.
A student is considered absent if: a) s/he does not have complete PPE and/or b)
s/he comes to class 30 minutes after the class has started. An absence, whether
excused or unexcused, merits a student a grade of 0 for laboratory performance. No
make-up experiments are allowed for any type of absences. For excused absences,
however, the student will still be allowed to submit the required report for the
experiment.
Absence during an examination merits the student a grade of INC.
Monitors
Monitors will be assigned for each experiment. It is the duty of the monitor to:
(a) borrow and return all floating glassware and equipment needed by the class for
each experiment, (b) lead and manage solution preparation for the whole class, (c)
maintain proper decorum and cleanliness of the class during the experiment, and (d)
check if the laboratory room is in order and all lockers are secured at the end of
the class.
Overtime
Overtime during experiments is not tolerated.
Broken Glassware and Equipment
Broken glassware and/or equipment should be replaced within a week from occurrence
of damage.
Data Sheets
The data sheets are found at the end of the laboratory manual. All needed data must
be presented after the experiment. The instructor’s copy of the data sheet should
be submitted to the instructor at the end of each experiment. It will be checked by
the instructor at the end of the period. On the other hand, the student’s copy of
the data sheet will be submitted along with the calculated results and report (ATQ
Report or Formal Report). Only blue or black pens must be used for filling the data
sheet. Pencils and liquid erasers are not allowed. If an entry is found to be
wrong, it should be struck-through and signed, before being replaced by the correct
data.
Post-Laboratory Reports
Each student must submit the completed data sheet and a laboratory report (either
an ATQ or an FR) ONE WEEK AFTER THE LAST DAY OF THE EXPERIMENT BEFORE THE CLASS
STARTS. Late submission gives the student a grade of 0 for the ATQ/FR of that
experiment. Non-submission of a report gives the student a grade of INC, if the
total standing of the student is passing.
(2017 Edition)
Answers to Questions (ATQ) Report
Each student will be required to submit Answers to Questions (ATQ) Reports during
the semester. It should be typewritten or handwritten on an A4 paper (refer to
format for printing specifications). The ATQ must contain the following: (a)
elaborate explanation of answers in essay form, (b) tabulated report of values if
needed, (c) working equations and sample calculations, and (d) the data sheet.
Questions to be answered are found at the end of each experiment. Additional
questions may be given by the instructor if he/she deems it necessary. Each ATQ
should have at least three print references. ATQ reports do not have abstract.
Formal Report (FR)
Each student will be required to submit two formal reports, one done individually
and the other one done by pair/group. The FR is typewritten on an A4 paper with the
following specifications: 1” margin on all sides and single spaced. The report
should only be three to five (3-5) pages long, excluding the appendix. The format
of the FR is provided in the following pages. The FR should include the following:
a) Abstract (a condensed version of the entire report)
b) Introduction (background information about the experiment)
c) Methodology
d) Results and Discussion
e) Conclusions and Recommendations
f) References
Each FR should have at least five references. The report must also include an
appendix for other data, working equations, sample calculations, etc.
As guide for students in correct scientific paper writing, a trial FR will be
submitted. This will serve as training for students in writing an FR. However, this
trial FR will be graded as an ATQ report.
Academic Dishonesty
Academic dishonesty (copying in examination, plagiarism, among others) is not
tolerated. A student caught to be performing academic dishonesty acts shall be
given a grade of 5.0 and may be subjected to disciplinary action by the University.
Plagiarism
(Reference: University of Washington Psychology Writing Center. 1997. Plagiarism
and Student Writing. Web. 2013.
<http://www.psych.uw.edu/writingcenter/writingguides/pdf/plag.pdf>)
Plagiarism occurs when one uses the ideas or writings of another as his/her own
without giving due credit. A student commits plagiarism by any of the following:
a) using another writer’s words without proper citation,
b) using another writer’s ideas without proper citation,
c) citing your source but reproducing the exact words of a printed source without
quotation marks,
d) borrowing the structure of another author’s phrases or sentences without
crediting the author who wrote it,
e) borrowing all or part of another student’s paper, or using someone else’s
outline to write your own paper, and
f) using a paper writing service or having a friend write the paper for you.
Examinations and Assessments
The course has three or four written assessments in the form of sit-in exercises or
long quizzes. Each sit-in exercise covers three or four experiments per assessment.
A practical exam will also be administered at the end of the semester.
J. Dela Cruz / Chemistry 26.1 (2016) P a g e | 1
ln
ln (1/T)(1/T)
1/T
1/T
Specified format for formal reports (Cambria 14)
J. Dela Cruz1 (Cambria 10.5)
1 Institute of Chemistry, College of Science, University of the Philippines,
Diliman, Quezon City 1101
Performed 10 June 2016; Submitted 12 June 2016
(1 space, Cambria 10)
ABSTRACT (Cambria 10, ALL CAPS)
A condensed version of the entire paper, summarizing the essential aspects of the
paper, significance of the study, purpose of the experiment, brief methodology,
major results, and major conclusions. This should be written in past tense and
third person. It should give the reader an idea of the scope of the study. Do not
include too much background information. Typically 100-200 words. Make the abstract
brief and concise.
Introduction (Cambria 10, Bold)
This must give the background information of the study. Give only relevant
information. Show the importance of the study. A summary of the procedure, as well
as objectives of the experiment must also be presented here. Include citation [1]
for all borrowed information. References must be arranged as they are used in the
report.
Introduction must be in third person (Cambria 10, justified)
Methodology (Cambria 10, Bold)
This summarized the procedure performed in the experiment in paragraph form (do not
include parts that were not done). It is in past tense form and passie voice. Do
not include diagram or procedural steps in preparing setups (Cambria 10, justified)
Results and Discussion (Cambria 10, Bold)
Present the results as they are discussed. Figures or tables which are not
discussed must be omitted. Place raw data in the appendix part. Rationalize the
methodology and the significance of each technique and reagent added. Organize data
into properly labeled tables, figures, etc., whichever is applicable. When
requiring regression curve, use an XY scatter plot and insert the regression curve.
The equation of the best fit curve must be presented in the discussion and not part
of the figure.
Each figure should have a brief caption describing it, along with symbols to aid
interpretation. Figures should be numbered sequentially, i.e., “Figure 1.”, “Figure
2.”, etc. and must be cited in the text as “figure 1,” “figure 2,” etc.
Tables and figures should be centered unless they occupy the full width of the
page. Captions should be placed on top of the table. Tables should be numbered
sequentially, i.e., “Table 1.”, “Table 2.”, etc. and should be referred to in the
text as “table 1,” “table 2,” etc.
Equations should be prepared using Equation Editor or MathType. Equations should be
numbered sequentially, i.e., (1), (2), etc., un-italicized and center-justified in
the text. (Cambria 10, justified)
Example:
One factor affecting the rate is the temperature as shown by the Arrhenius equation
(1) where k is the rate constant, A is the Arrhenius constant, Ea is the activation
energy, R is the gas constant and T is the temperature. Using this equation,
however, results to an exponential graph which makes interpolation harder. Hence,
the linearized form of the Arrhenius equation (2) was used to prepare figure 1.
k= Ae−EaRT (1)
lnk= −EaRT+lnA (2)
Figure 1 below shows that the plot of ln (1/T) and (1/T) is inversely proportional.
The equation of the line given by the figure is y = -4977x + 11.92 with linearity
value R2 equal to 0.998.
Figure 1. Effect of temperature on reaction rate by the Arrhenius equation.
Table 1. Calculated values for dissociation and stability constants.
A1
A2
A3
K1
4.64E-06
1.18E-05
2.4E-06
K2
2.00E-05
3.98E-06
2.81E-05
Analyze and interpret results. Include answers to guide questions for discussion.
Give the % error and propagation
for uncertainty, as well as pooled standard deviation and account for the
deviations, include sources of error.
Conclusion and Recommendations (Cambria 10, Bold)
Summary of important results should be shown here. Discuss degree of success or
failure of the experiment. Include recommendations for improvement. (Cambria 10,
justified)
References (Cambria 10, Bold)
[1] Caleja, H., 2010. How to Write a Formal Report. Quezon City: UP Diliman. 21-30.
(Author/s. Title of the book or journal. Year. City: Publisher. Page number.)
You may use other formats (MLA or APA citation). Each FR should have at least (5)
references. Minimum of (3) print references and maximum of (2) online sources.
Appendix (Cambria 10, Bold)
A. Answers to Questions (if necessary)
B. Figures (if necessary)
C. Raw Data Table (if necessary)
D. Working Equations
E. Sample Calculations
Other remarks:
• Maximum of four (4) pages (including references but excluding appendix)
• Appendix should still be paginated. A two column format should be followed in the
body until references. Appendix should follow single column format.
• Attach your data sheets when submitting your formal report
(2017 Edition)
EXPERIMENT 1
Application of Statistical Concepts in the Determination of
Weight Variation in Samples
OBJECTIVES
At the end of the experiment, the student should be able to:
1) use an analytical balance properly;
2) gain an understanding of some concepts of statistical analysis; and
3) apply statistical concepts in analytical chemistry.
INTRODUCTION
In dealing with the numerical results in an experiment, it is important to assess
both the accuracy and precision
of these data. Accuracy refers to the closeness of a measurement to the true or
accepted value. Precision refers
to the closeness of the measurements that have been obtained using the same method.
The accuracy and
precision of measurements are evaluated using statistical tests.
BASIC STATISTICAL CONCEPTS
Sample and Population
In statistics, population refers to the collection of all measurement of interest,
while sample refers to the subset of
population that is representative of the population from which it was collected.
Parameter (e.g., population
mean, population standard deviation) is a quantity that describes a property of the
population, while statistic
(e.g., sample mean X , sample standard deviation s) is a quantity that describes a
property of the sample. In the
absence of determinate errors, the statistic is considered as a good estimate of
the parameter. The reliability of
the statistic increases with the number of measurements used.
Measures of Central Tendency
Measures of central tendency are measures of the location of the center of a
distribution.
1. Mean
One of the most common measures of central tendency is the mean (or average).
�
=
Σ ��
��
=1
�
=
(�1 + �2 + �3 + ⋯ �� )
�
(1.1)
Xi represents the individual values of X making up a set of n replicate
measurements.
2. Median
The median is the middle value in a set of data that has been arranged in
increasing or decreasing order. The
median is useful when a set of data contains an outlier, a result that differs
significantly from the rest of the data
in the set. For an odd number of results, the median can be evaluated directly. For
an even number, the average
of the middle pair is used.
Measures of Accuracy
Accuracy is expressed in terms of absolute error or relative error.
1. Absolute Error, E
Absolute error is the difference between the experimental and true value. Xi is the
experimental value and Xt is
the true value.
� = �� − �� (1.2)
(2017 Edition)
2. Relative Error, Er
Relative error is the absolute error divided by the true value. Relative error is
usually expressed in percent.
��=��−��×100%
(1.3)
Measures of Precision
1. Variance, s2
Variance is a more statistically useful measure of precision.
�2=Σ(��−�)2��=1�−1
(1.4)
2. Standard Deviation, s
Standard deviation is just the square root of the variance.
� =√Σ(��−�)2��=1�−1
(1.5)
Note that for large values of n, the number of degrees of freedom, (n – 1),
approaches n. Consequently, the sample standard deviation approaches the population
standard deviation.
� =√Σ(��−�)2��=1�
(1.6)
3. Relative Standard Deviation, RSD
Standard deviation is frequently reported in relative rather than absolute terms.
Relative standard deviation is often expressed in parts per thousand (ppt).
��=��×1000 ��
(1.7)
4. Coefficient of Variation, CV
When the relative standard deviation is in percent, it is called the coefficient of
variation.
��=��×100 %
(1.8)
5. Pooled Standard Deviation, spooled
When several small sets have the same sources of indeterminate error (i.e., the
same type of measurement but different samples), the standard deviations of the
individual data sets may be pooled to more accurately determine the standard
deviation of the analysis.
��=√Σ(��−�1)2+Σ(��−�2)2+Σ(��−�3)2�3�=1�2�=1�1�=1�1+�2+�3+...−��
(1.9)
where n1 is the number of data in set 1, n2 is the number of data in set 2, and so
forth. The term ns is the number of data sets that are being pooled.
6. Range, R
Range is the difference between the highest and lowest value in a set of
measurements.
�=�ℎ��ℎ��−��
(1.10)
(2017 Edition)
7. Relative Range, RR
Range may also be expressed in relative terms.
��=��×1000 ��
(1.11)
Confidence Interval, CI
Confidence interval provides a range of values within which the population mean is
expected to lie at a specified confidence level. The boundaries of the confidence
interval are called confidence limits.
��=�±��√�
(1.12)
t is dependent on the confidence level and degrees of freedom. The 95% level which
incorporates about two standard deviation units is often used in getting the
confidence interval.
Table 1.1. Values of t for various levels of probability.
n-1
1
2
3
4
5
6
7
8
9
10
T90%
6.31
2.92
2.35
2.13
2.02
1.94
1.90
1.86
1.83
1.81
T95%
12.7
4.30
3.18
2.78
2.57
2.45
2.36
2.31
2.26
2.23
T99%
63.7
9.92
5.84
4.60
4.03
3.71
3.50
3.36
3.25
3.17
Grubbs’ Test
An objective criterion must be used in rejecting suspected outliers. Grubbs’ test
is one of the most commonly used for detecting outliers. This test is applicable
only for data sets containing one suspected outlier. The experimental value, g, is
calculated and compared with tabulated critical g values.
��=|��−�|�
(1.13)
Xi is the questionable measurement, � is the mean, s is the standard deviation of
the whole data set. The suspected outlier can be rejected if g exceeds the
tabulated g value. A table for critical g values for 3 to 10 measurements at 95%
and 99% confidence level is given below:
Table 1.2. Critical Values for the Grubbs’ Test.
N
3
4
5
6
7
8
9
10
g95%
1.1543
1.4812
1.7150
1.8871
2.0200
2.1266
2.2150
2.2900
g99%
1.1547
1.4962
1.7637
1.9728
2.1391
2.2744
2.3868
2.4821
MATERIALS
(10) 25-centavo coins
Forceps or crucible tongs
GLASSWARE
Watch glass
EQUIPMENT
Analytical balance
PROCEDURE
Weighing of Samples
1. Place the ten coins on a watch glass using forceps.
2. Take the weight of each coin using "weighing by difference" method (refer to
Appendix 2).
3. Record the weights of the coins in your data sheet.
(2017 Edition)
EXPERIMENT 2
Solution Preparation
OBJECTIVES
1) perform stoichiometric calculations needed in the solution preparation;
2) know the proper way of preparing solutions from solid and liquid reagents;
3) know the proper pieces of glassware and equipment to in solution preparation;
and
4) calculate the exact concentration of the prepared solution from standardization.
INTRODUCTION
Many of the reactions utilized for quantitative analysis take place in aqueous
solutions. In aqueous solution, the species present are in a small state of
subdivision, such that solutes exist as ions rather than aggregates of these. In
this manner, the particles are free to move about the solution and a proportion of
the ensuing collisions between solute particles result in a reaction. Such
solutions may be prepared in two ways, depending on the nature of the solute,
whether solid or liquid.
The most common way of preparing solutions of different concentrations is by
dissolving a weighed amount of solid in enough solvent to produce a solution of
specific volume. Weighing may be done with the use of a top loading balance or an
analytical balance depending on the accuracy sought for.
Another way of solution preparation is by dilution. This method requires
measurement of a specific volume of solute and rendering it less concentrated by
addition of water until a solution of desired volume is achieved. The most
appropriate way of volume measurement is with the use of a graduated cylinder or a
pipette (volumetric/transfer or measuring), again, depending on the accuracy sought
for. A volumetric pipette is used for accurate measurements since it is designed
and calibrated to deliver only one volume while a measuring pipette is calibrated
into small divisions allowing measurement of various amounts of liquid. Volumetric
flasks are also used to prepare the above mentioned solutions. The concentrations
of such solutions may be expressed in any manner appropriate, as discussed in the
ways of expressing concentration, usually in molarity (M) or parts per million
(ppm).
In the laboratory, there are cases when the intended concentrations of the
solutions to be used are too dilute such that measurement of small masses or
volumes seems impossible with the balances and glassware available. In such
situations, it is wiser for the analytical chemist to prepare a solution of
relatively higher concentration (a stock solution), measure out an appropriate
volume (an aliquot) andthen further dilute it to prepare the solution of desired
(lower) concentration.
Example: Preparation of 100.0-mL 0.0100M NaCl directly from NaCl solids.
( 0.0100M )( 0.100 L)( 58.44 g/mol ) NaCl = 0.0584 g
NOTE: The amount to be weighed is too small and weighing may be prone to errors.
Instead, prepare 100.0-mL 0.1000M NaCl first.
( 0.1000M)( 0.100 L)( 58.44 g/mol) NaCl = 0.5840 g
NOTE: Larger amount is more convenient to weigh.
Weigh the desired amount in a beaker. Add enough distilled water to dissolve the
solid then transfer quantitatively to 100.0-mL volumetric flask. Dilute to mark
with distilled water to yield 0.1000 M NaCl solution.
(2017 Edition)
To prepare 100.0-mL 0.0100 M NaCl from 0.1000 M NaCl,
M1V1 = M2V2
(V1)(0.1000 M ) = ( 100.0 mL )( 0.0100 M )
V1 = 10.0 mL of the 0.1000 M NaCl stock solution prepared
measure out an aliquot of the stock solution and dilute to 100.0 mL (the desired
volume) with water in a volumetric flask.
For sample analysis, there are cases when the analyte present in the sample exists
in high concentrations such that dilution, as described above, is also necessary.
Example: Determination of [Ca2+] in drinking water
Twenty (20.00) mL of drinking water was measured and diluted to 100.0 mL. The
diluted aliquot was analyzed via a known titrimetric method (Experiment 7:
Complexometric Titration). By applying the appropriate volumetric calculation, the
concentration of the analyte in the diluted sample (100.0 mL solution) may be
determined.
Problem: How to calculate the [Ca2+]original in the 20.00 mL sample?
Solution: Use DILUTION FACTOR
�� ,��= ��
(2.1)
(� �� 2+� �� )(100.0 �� 0.02 � (��/��))=� �� 2+� �� (��/�� )
NOTE: Expect that the calculated concentration of the original solution is HIGHER,
(more concentrated). Notice how the calculation resembles dimensional analysis.
There are also cases when a series of dilutions have been performed such that two
or more DFs are necessary.
There are also cases when the concentration of the original solution is known and
the concentration of a diluted solution is to be determined (opposite of the
example above). For this type of calculation, an ALIQUOT FACTOR may be utilized.
�� ,��= �� =1��
(2.2)
(� �� 2+� �� )(20.00 �� 0.10 � �� )=� �� 2+� ��
NOTE: Expect that the calculated concentration of the original solution is LOWER
(less concentrated). Notice how the calculation resembles dimensional analysis.
There are also cases when a series of dilutions have been performed such that two
or more AFs are necessary.
The exact concentration of the prepared solution can then be determined by
standardization. In standardizing solutions, a primary standard is weighed with
high accuracy, dissolved and then titrated with the solution until the endpoint is
reached. A primary standard should be a stable solid with high purity and high
molecular weight with a known chemical reaction with the solution to be
standardized.
In this experiment, solutions of NaOH and HCl will be prepared to illustrate ways
of solution preparation described above. Afterwards, standardization of HCl and
NaOH, using Na2CO3 and KHP as primary standards, respectively, will then be done to
determine the exact concentration of the standard solutions.
(2017 Edition)
CHEMICALS
concentrated HCl
Na2CO3, primary standard
NaOH
Phenolphthalein
KHP, primary standard
GLASSWARE
Volumetric flasks (100-, 250-mL)
Beakers (250-mL)
Droppers
Erlenmeyer flasks (250-mL)
Volumetric pipette (25-mL)
Spatula
EQUIPMENT
Analytical balance
Top loading balance
PROCEDURE
Preparation of 100.0 mL 1.0 M sodium hydroxide solution from solid
1. Calculate the mass of NaOH pellets needed to prepare a solution with a
concentration of 1.0 M.
2. Using a clean and dry 250-mL beaker, weigh the calculated mass of NaOH pellets
using top loading balance.
NOTE: An analytical balance is not suitable in weighing NaOH pellets since it is
hygroscopic.
3. Add enough distilled water to dissolve the pellets and stir. The dissolution is
exothermic, so cool the solution in a water bath if necessary.
4. When completely dissolved, transfer quantitatively into a 100-mL volumetric
flask using distilled water to wash the beaker. Add enough distilled water to make
a volume of about 90.0 mL. Cover and cool the flask and solution to room
temperature.
5. Bulk the solution to the mark with distilled water and cover. Mix the solution
thoroughly by repeated shaking and inversion of the flask.
6. Transfer the solution into a dry and clean plastic bottle and label properly.
NOTE: Never store any solution in a volumetric flask as it is not a storage
container. Never store NaOH or any basic solutions in glass containers.
Preparation of 50.0 mL 3.0 M hydrochloric acid solution by dilution
1. Calculate the volume of concentrated HCl needed to prepare a solution of 3.0 M
HCl.
2. Pipette out the calculated volume of concentrated HCl solution into a 50-mL
volumetric flask containing about 10.0 mL of distilled water.
NOTE: Always add concentrated acid to water; never water to acid when diluting acid
solutions. Add enough distilled water to make a volume of about 40.0 mL. Swirl to
mix, cover the flask and cool the solution to room temperature, if necessary.
4. Transfer the solution into a dry and clean reagent bottle and label properly.
(2017 Edition)
EXPERIMENT 3
Iodine Clock Reaction
OBJECTIVES
1) describe the kinetics of the reaction of I- and S2O82-;
2) use the initial rate method to determine the rate law of the reaction;
3) observe the effect of temperature on the reaction rate and calculate pertinent
values of the Arrhenius equation; and
4) observe the effect of a catalyst to the reaction rate.
INTRODUCTION
The rate of a chemical reaction is defined as the change of the concentration of a
reactant or product per unit time. The concentration of the reactants, temperature,
and the presence of catalyst are the major factors that affect the rate of a
chemical reaction.
The kinetics of the reaction between persulfate, S2O82-, and iodide, I- ions will
be studied in this experiment:
S2O82-(aq) + 2I-(aq) → 2SO42-(aq) + I2 (aq)
(3.1)
The rate expression of this reaction can be written as the decrease of
concentration of S2O82-/ I- or the formation of the products SO42-/ I2 with time.
This is given in the following rate law:
��=−�[�2�82−]��=−12�[�−]��=12�[��42−]��=�[�2]��=�[�2�82−]�[�−]�
(3.2)
where k is the rate constant and the powers x and y give the order of the reaction
with respect to S2O82- and I-, respectively. These variables can be determined
experimentally using the method of initial rates. Such method involves performing
the reaction at controlled conditions, i.e. varying concentrations of one reactant
while keeping the concentration of the other constant, and measuring the rate at
each case.
The effect of temperature on the reaction rate is given by the Arrhenius equation:
ln�=ln�−��
(3.3)
where A is the Arrhenius constant, Ea is the activation energy of the reaction, T
is temperature in Kelvin, and R is the universal gas constant (8.314 J mol-1 K-1).
From the rate constants and reaction temperatures, Ea and A of the reaction of
S2O82- and I- can be determined.
In this experiment, the rate of I2 formation will be measured to describe the rate
of the reaction. The I2 formed from the S2O82-/I- reaction is reduced back to I- by
S2O32- ions.
2S2O32-(aq) + I2(aq) → S4O62-(aq) + 2I-(aq)
(3.4)
When all the S2O32- is used up, free I2 starts to form in solution. By measuring
the time taken for the known amount of S2O32- to be consumed, the rate of the
formation of I2 during that time can be calculated.
MATERIALS/APPARATUS
Ice
Stopwatch/timer
Thermometer
(2017 Edition)
CHEMICALS
KI
KCl
K2SO4
K2S2O8
Na2S2O3∙5H2O
CuSO4·5H2O
Starch
GLASSWARE
Measuring pipettes (10-mL)
Beakers (50-mL)
EQUIPMENT
Top loading balance
Hotplate
PROCEDURE
Prepare the following solutions by class:
1. 500.0 mL 0.2 M KI
2. 500.0 mL 0.2 M KCl
3. 500.0 mL 0.1 M K2S2O8
4. 500.0 mL 0.1 M K2SO4
5. 500.0 mL 4.0 mM Na2S2O3 (from Na2S2O3∙5H2O)
6. 20.0 mL of 1% (w/v) fresh starch solution
a. Moisten 0.20 g of soluble starch with a small amount of H2O until a smooth paste
is obtained.
b. Pour slowly into 20.0 mL of boiling water. The starch solution must be freshly
prepared.
NOTE: Keep the solution at 90°C-100°C to avoid starch solution from drying up.
7. 50.0 mL 0.01 M CuSO4 (from CuSO4·5H2O)
Effect of Persulfate and Iodide Concentrations on the Reaction Rate
1. Prepare the contents of beakers A and B according to the volumes presented in
the following table:
Table 3.1. The different runs for the effect of persulfate and iodide
concentrations on reaction rate.
Run a
Beaker A
Beaker B (+ 3 drops of fresh starch)
0.2 M KI, mL
0.2 M KCl, mL
0.1 M K2S2O8
0.1 M K2SO4
4.0 mM Na2S2O3
1
10.0
0.0
5.0
5.0
5.0
2b
5.0
5.0
5.0
5.0
5.0
3
2.5
7.5
5.0
5.0
5.0
4
5.0
5.0
7.5
2.5
5.0
5
5.0
5.0
10.0
0.0
5.0
a Condition: room temperature
b will be referred to as set 1 of run 2 (two more sets will be prepared in Part C)
2. Pour the contents of beaker A into beaker B. Immediately start timing the
reaction. Stop the timer once the mixture turns blue. Measure the temperature of
the reaction mixture.
NOTE: Runs 1-5 SHOULD be done one at a time. For each run, label two 50-mL beakers
as “A” and “B.”
Effect of Temperature on the Reaction Rate
1. Prepare two more sets of “run 2” (referred to as sets 2 and 3).
2. In a water bath, heat beakers A and B of run 2 (set 2) at around 50°C (40°C-
60°). Mix the contents of beaker A and beaker B. Immediately start timing the
reaction until the mixture turns blue.
3. Cool beakers A and B of run 2 (set 3) in an ice bath. Once the temperature has
already reached around 5 0C (0°C-10°C), pour the contents of beaker A into beaker B
and start timing the reaction. Stop the timer after a blue solution is observed.
(2017 Edition)
Effect of Catalyst on the Reaction Rate
1. Prepare a fourth set of run 2.
2. Add 4 drops of 0.01 M CuSO4 immediately after the contents of beaker A is added
to the contents of beaker B. Time the reaction until the reaction mixture turns
blue. Compare the reaction time with set 1.
WASTE DISPOSAL
1. Dispose of Cu(II) solutions into the inorganic waste jar.
2. All other solutions can be discarded in the sink along with copious amounts of
water.
(2017 Edition)
EXPERIMENT 4
Common Ion Effect and Buffers
OBJECTIVES
1) understand and relate the concepts of common-ion effect and buffer solutions;
2) distinguish buffer solutions from other types of solutions;
3) perform calculations related to the buffer concept; and
4) observe the effect of dilution on the pH of a buffered sample.
INTRODUCTION
Acid-base indicators are weak acids or bases whose conjugate ions have different
colors with respect to their neutral molecules. Consider a hypothetical indicator,
HInd, ionizing as follows,
HInd(aq) + H2O(l) ⇌ H3O+(aq) + Ind-(aq)
Color A Color B
(4.1)
where HInd is a weak acid with Color A and Ind- is the conjugate base with Color B.
Within a certain pH range, approximately equal amounts of HInd and Ind- are
present. Thus, the solution will have a color intermediate between Color A and
Color B. Below this pH range, the HInd form predominates and the solution will
exhibit Color A. Above this range, the form Ind- predominates and the solution will
show Color B. For instance, indicators such as methyl orange and phenolphthalein
have different colors at some pH ranges.
Table 4.1. Colors of indicators at certain pH ranges.
Indicator
pH Values
Color
Methyl Orange
pH < 3.1
Red
3.1 < pH < 4.5
Salmon pink
pH > 4.5
Yellow
Phenolphthalein
pH < 8.3
Colorless
8.3 < pH < 10.0
Very light pink
pH > 10.0
Red
The pH of a solution can be estimated by adding a few drops of an indicator
solution to it and observing the resulting color. The exact pH may be determined by
means of a calibrated pH meter (refer to Appendix 2).
In accordance with the Le Chatelier’s principle, addition of the products of a
reaction to a system at equilibrium causes the equilibrium to shift towards the
formation of the reactants. Consider HA as a weak acid and thus the equilibrium,
HA(aq) + H2O(l) ⇌ H3O+(aq) + A-(aq)
(4.2)
is shifted in the direction of HA by the addition of a common ion. Addition of a
strong acid increases H3O+ or addition of a salt containing anion A- suppresses the
ionization of HA.
Similarly, the addition of a strong base or a salt containing the cation BH+ to a
solution of B, a weak base shifts the equilibrium towards B, lowering the degree of
ionization of B
B(aq) + H2O(l) ⇌ BH+(aq) + OH-(aq)
(4.3)
A buffer is a solution which resists an appreciable change in pH upon addition of
small amounts of strong acid or strong base. An example of this is a solution which
contains a weak acid or weak base with their respective conjugate ions. Given this
condition, a solution containing B and BH+ is a buffer. Likewise, a solution
containing HA and A- is also an example. Given below are the equations which show
the buffer action of:
(2017 Edition)
1. HA–A - Buffer
a. Ionization of the weak acid HA HA + H2O ⇌ H3O+ + A- (4.4)
b. Effect of the addition of strong acid A- + H3O+ → H2O + HA (4.5)
(neutralization of H3O+)
c. Effect of the addition of strong base HA + OH- → H2O + A- (4.6)
(neutralization of OH-)
2. B:- BH+ Buffer
a. Ionization of the weak base B B + H2O ⇌ BH+ + OH- (4.7)
b. Effect of the addition of strong acid B + H3O+ → H2O + BH+ (4.8)
(neutralization of H3O+)
c. Effect of the addition of strong base BH+ + OH- → H2O + B (4.9)
(neutralization of OH-)
To illustrate how a buffer works, consider a buffer composed of a weak acid (HX)
and one of its salts (MX, where M+ could be Na+, K+, or other cations). The acid-
dissociation equilibrium in this buffered solution involves both the acid and its
conjugate base:
H2O(l) + HX(aq) ⇌ H3O+(aq) + X-(aq)
(4.10)
The corresponding acid-dissociation-constant expression is
��= [�3�+][�−][��]
(4.11)
Evaluating the value of [H+] leads to,
[�3�+]= ��[��][�−]
(4.12)
It is seen from this expression that [H3O+], and thus the pH, is determined by two
factors: the value of Ka for the weak-acid component of the buffer, and the ratio
of the concentrations of the conjugate acid-base pair, [HX] / [X-]
If OH- ions are added to the buffered solution, they react with the acid component
of the buffer
OH-(aq) + HX(aq) ⇌ H2O(l) + X-(aq)
(4.13)
This reaction causes [HX] to decrease and [X-] to increase. However, as long as the
amounts of HX and X- in the buffer are large compared to the amount of OH- added,
the ratio [HX] / [X-] doesn’t change much, and thus the change in pH is small.
If H3O+ ions are added, they react with the base component of the buffer:
H3O+(aq) + X-(aq) ⇌ HX(aq) + H2O(l)
(4.14)
Using either of the two equations, it is observed that the reaction causes [X-] to
decrease and [HX] to increase. As long as the change in the ratio [HX] / [X-] is
small, the change in pH will be small.
(2017 Edition)
Buffer capacity is the amount of acid or base the buffer can neutralize before the
pH begins to change to an appreciable degree. The capacity of a buffer is within a
certain range: pH = pKa ± 1 or pOH = pKb ± 1. This capacity depends on the amount
of acid and base from which the buffer is made.
The pH of a buffer depends on the Ka for the acid and on the relative
concentrations of the acid and base that comprise the buffer. An alternate approach
used to calculate the pH of a buffer is the Henderson-Hasselbalch equation:
��=��+ ��([��][��])
(4.15)
where [acid] and [base] refer to the initial concentrations of the acidic and basic
components of the buffer, respectively. Henderson-Hasselbalch equation assumes that
the initial concentrations of the acidic and basic components are approximately
equal to their equilibrium concentrations. That is, the dissociation of the acidic
component is negligible.
Another form of the Henderson-Hasselbalch equation is
��=��+ ��([��][��])
(4.16)
CHEMICALS
CH3COOH
NH3
HCl
NaOH
NaCH3COO
NH4Cl
Phenolphthalein
Methyl orange
GLASSWARE
Volumetric flasks (250-,100-mL)
Beakers (50-mL)
Volumetric pipettes
EQUIPMENT
pH meter
PROCEDURE
Prepare the following solutions by group:
1. 50.0 mL 0.20 M CH3COOH
2. 50.0 mL 0.10 M CH3COOH
3. 50.0 mL 0.20 M NH3
4. 50.0 mL 0.10 M NH3
5. 25.0 mL 0.20 M NaCH3COO
6. 25.0 mL 0.20 M NH4Cl
1. 100.0 mL 1.0 M NaOH
2. 100.0 mL 1.0 M HCl
NOTE: Use the 1.0 M NaOH solution and 3.0 M HCl solution from the Solution
Preparation experiment.
pH using Visual Indicators and pH Meter
1. Place the indicated volumes of the following solutions in separate 50-mL
beakers:
Solution 1: 30.0 mL 0.10 M CH3COOH
Solution 2: 15.0 mL 0.20 M CH3COOH – 15.0 mL 0.20 M NaCH3COO
(2017 Edition)
Solution 3: 30.0 mL 0.10 M NH3
Solution 4: 15.0 mL 0.20 M NH3 – 15.0 mL 0.20 M NH4Cl
2. Cover each beaker with a watch glass.
3. To Solutions 1 and 2, add one drop of methyl orange indicator. Compare and
record the colors of the solutions.
4. To Solutions 3 and 4, add one drop of phenolphthalein indicator. Compare and
record the colors of the solutions.
5. Measure the pH of Solutions 1 to 4 using a properly calibrated pH meter. Record
the pH reading of each solution.
Effect of Strong Acid or Strong Base on Buffers
1. Divide Solution 1 in Part A into three equal portions. To the first portion
(Solution 1a) add three drops of 1.0 M HCl solution. To the second portion
(Solution 1b) add three drops of 1.0 M NaOH solution. Compare the colors of the two
with the third portion (Solution 1c).
2. Approximate the pH from the colors of the solutions and record.
3. Measure and record the pH using the pH meter.
4. Repeat steps 1 to 3 with the other solutions (Solutions 2, 3, and 4).
WASTE DISPOSAL
1. Discard excess concentrated acids and bases into their respective waste bottles.
2. Drain and flush excess diluted solutions into the sink with copious amounts of
water.
(2017 Edition)
EXPERIMENT 5
Determination of the Solubility Product Constant of Calcium Hydroxide
OBJECTIVES
1) determine the Ksp of calcium hydroxide; and
2) explain the effects of common and diverse ions on solubility of sparingly
soluble salts.
INTRODUCTION
When a slightly soluble ionic solid is placed in water, equilibrium is soon
established between the excess solid and the ions in the saturated solution. For
example, the hypothetical ionic solid AxBy is in contact with its saturated
solution, the equilibrium is:
AxBy(s) ↔ xAy+(aq) + yBx-(aq)
(5.1)
and
Ksp = [Ay+]x [Bx-]y
(5.2)
where the equilibrium constant, Ksp, is called the solubility product constant of
AxBy(s) and the expression [Ay+]x [Bx-]y is the ion-product, IP, or the reaction
quotient, Q, when the concentrations used are initial concentrations. Compared to
other equilibrium expressions, it is noticeable that the solid itself does not
appear as a denominator in the Ksp expression. It is because the activity of any
solid is equal to one. Thus, writing the Ksp expression for saturated and
heterogenous solution, the concentration of solids is ignored. However, like all
equilibrium constants, Ksp is temperature dependent.
The Ksp value may be used as a measure of solubility, and the relation between IP
of the solution and the Ksp can be used as a criterion if precipitation will happen
or not. When Ay+ ions were added to a solution containing Bx- ions:
the resultant solution is unsaturated if IP < Ksp,
the reaction mixture is saturated if IP = Ksp,
precipitation is observed if IP > Ksp.
Other factors, such as presence of common ions in the solution and ionic strength
of the medium, also affect the molar solubility of a compound. A common ion is an
identical ion from another substance that is also present in the solution.
According to Le Chatelier’s principle, the presence of a common ion shifts the
direction of the equilibrium to the reactant side. Therefore, the concentration of
the common ion should be taken into account when determining solubility.
However, when other ion or electrolyte from a substance containing no common ion
with the sample is present in the solution, the resultant increase in the ionic
strength of the solution is what is accounted in the solubility of the compound.
The ionic strength, μ, of the solution depends on the charges and the
concentrations of all the ions present in the solution,
�= 12 Σ��2
(5.3)
where Ci and Zi are concentrations (in molarity) and charges of the ions,
respectively.
(2017 Edition)
For example, the ionic strength of a 0.1 M Na2SO4 solution is: μ= 12 (C��+
(Z��+)2+C��42−(Z��42−)2 ) μ= 12 ((0.20)(1)2+(0.10)(−2)2 ) μ=0.30
In the experiment, the Ksp of calcium hydroxide, Ca(OH)2 will be determined by
calculating for the [OH-] from a saturated solution of Ca(OH)2 through acid-base
titration.
Ksp = [Ca2+][OH-]2
(5.4)
The effect of common ion and change in ionic strength of the solution to the
solubility of Ca(OH)2(s) will also be evaluated.
APPARATUS
Iron stands & rings
Burette clamps
Filter paper
CHEMICALS
HCl, concentrated
Ca(OH)2
Phenolphthalein
KCl
CaCl2
GLASSWARE
Beakers (100-, 250-mL)
Measuring pipettes
Volumetric pipettes (10-, 25- mL)
Burettes (50-mL)
Volumetric flasks (250-,1000-mL)
Graduated cylinder (100-mL)
Funnels
EQUIPMENT
Analytical balance
Top loading balance
Hotplate
PROCEDURE
NOTE: Boiled distilled water is needed for standardization of HCl.
1. 1.00 L 0.10 M HCl
NOTE: Use the 3.0 M HCl solution from the Solution Preparation experiment.
2. 250.0 mL 1.0 M stock KCl
3. 250.0 mL each 0.50 M, 0.25 M, 0.10 M, 0.05 M, 0.01 M KCl solution from stock 1.0
M KCl solution.
4. 250.0 mL 0.010 M CaCl2
Standardization of 0.10 M HCl
1. Take three (3) clean and properly labeled 250-mL Erlenmeyer flasks. Into the
three flasks, weigh 0.1 g of the primary standard Na2CO3 to the nearest 0.1 mg.
Record the weights of the primary standard.
2. Add about 75.0 mL of boiled distilled water and swirl to dissolve the solids.
3. Add 2 to 3 drops of phenolphthalein indicator. Record the initial burette
reading and titrate with the prepared 0.10 M HCl solution until phenolphthalein
endpoint.
4. Record the final burette reading for each titration in your data sheet.
(2017 Edition)
Determination of Ksp and Molar Solubility
1. Add Ca(OH)2 to 250.0 mL distilled water with stirring until equilibrium is
achieved.
2. Filter the undissolved precipitate. Measure out 50.0 mL of the supernate into a
250-mL Erlenmeyer flask using a pipette.
3. Add a few drops of phenolphthalein indicator and titrate with standardized HCl
solution until endpoint is achieved.
4. Record the volume the HCl solution used. Perform two more trials.
Effect of Common Ions on the Solubility of Ca(OH)2
1. Add Ca(OH)2 to 250.0 mL of 0.010 M CaCl2 with stirring until equilibrium is
achieved.
2. Filter the undissolved precipitate. Measure out 50.0 mL of the filtrate in a
250-mL Erlenmeyer flask.
4. Record the volume of HCl solution used. Perform two more trials.
Effect of Ionic Strength on the Solubility of Ca(OH)2
1. Add Ca(OH)2 to 250.0 mL volumes of 0.50 M, 0.25 M, 0.10 M, 0.05 M, 0.01 M KCl
with stirring until equilibrium is achieved.
2. Filter the undissolved precipitate. Measure out 50.0 mL of the filtrate in a
4. Record the volume HCl solution used. Perform two more trials.
NOTE: Do not discard excess HCl solution. Store it in a glass bottle for future
use.
WASTE DISPOSAL
1. Collect excess HCl solution. Use this to dissolve all Ca(OH)2 precipitate.
Dilute the resulting solution with plenty of water and flush directly down the sink
with copious amounts of water.
2. Dispose of all titrated solution into the sink with copious amounts of water.
3. Dispose of all used filter papers in the solid waste container.
(2017 Edition)
EXPERIMENT 6
Quantitative Determination of Soda Ash Composition by Double Indicator Titration
OBJECTIVES
1) determine the composition of the soda ash sample and respective percentage in
the sample,
2) relate the experiment to the following concepts: (a) strong acid-strong base and
strong acid-weak base titrations, (b) carbonate system titration, and (c) double-
indicator titration, and
3) perform calculations involving simple and complex acid-base titrations and in
particular those dealing with carbonate-like systems.
INTRODUCTION
Volumetric or titrimetric methods are processes that involve the reaction of a
standard solution of known amounts with an unknown solution or analyte to determine
the stoichiometric or equivalence point. If the details of the reaction are well-
defined and the equivalence point is accurately located, then the amount of the
unknown or analyte present can be calculated from the known amount of the standard
solution used in the reaction.
In any volumetric analysis, a reference material is most important as the accuracy
of the method is dependent on it. This reference material is the primary standard
upon which one determines the accurate concentration of the standard solution.
Standard titrants in acid-base titrations are generally strong acids or strong
bases. In aqueous solutions, weak acids and bases are not suitable due to the pH
change that takes place near the equivalence point. The most commonly used acid is
hydrochloric acid and for the base, sodium hydroxide.
Acid-base titration is based on neutralization reaction, this is also called
acidimetric or alkalimetric titration. It is a simple reaction of a proton and a
hydroxyl ion as given by the ionic reaction:
H3O+(aq) + OH-(aq) → 2H2O(l)
(6.1)
Simple systems usually involve monofunctional acids or bases. Mixtures of acids or
bases and polyfunctional acids or bases are considered complex systems. Such
complex systems usually contain two or more acidic or basic species.
In this experiment, titration of complex systems will be observed. With
hydrochloric acid as titrant, the primary standard used for the standardization is
sodium carbonate with high purity. The carbonate ion reacts with the acid according
to the successive acid-base reactions:
CO32-(aq) + H3O+(aq) → HCO3-(aq) + H2O(l)
(6.2)
HCO3-(aq) + H3O+(aq) → H2CO3(aq) + H2O(l) ↔ CO2(g) + 2H2O(l)
(6.3)
It is a two component system wherein the second component is a product of the first
reaction. The first component is the carbonate ion (CO32-) and the second is the
bicarbonate ion (HCO3-). Following stoichiometry, it can also be deduced that the
amount of H3O+ in reactions (6.2) and (6.3) are equal. The first equivalence point
(6.2) can be seen using phenolphthalein indicator with a color transition from pink
to colorless. Moreover, the second equivalence point (6.3) can be seen using methyl
orange indicator.
(2017 Edition)
In this analysis, the unknown sample may be a pure compound of sodium carbonate,
sodium bicarbonate or sodium hydroxide or a compatible mixture of the three. A
mixture of sodium hydroxide and sodium bicarbonate are incompatible due to their
properties. The analysis of the unknown sample will need a two-titration or a
double indicator titration. In this case, a double indicator titration will be
used. The indicators to be used should change color at different pH ranges, to
signal neutralization of different protons of the complex system. The first
reaction involves reactions (6.1) and (6.2) where the phenolphthalein indicator
changes color; while the second reaction involves reaction (6.3) where the methyl
orange indicator changes color. Thus, to resolve the possible components of an
unknown sample requires comparison of the volume of HCl required reaching these two
distinct endpoints, the Vph and Vmo, as shown in Figure 6.1.
Figure 6.1. A graph of pH against volume of HCl titrant for reactions involving
carbonate and carbonate-like systems.
Table 6.1 gives the volume relationships in the analysis of soda ash using double
indicator titration method.
Table 6.1. The volume relationships for different compositions of soda ash.
Substance composition
Relation between Vph and Vmo
Amount of substance present
NaOH
Vmo = 0; Vph > 0
MVph
Na2CO3
Vph = Vmo
MVph or MVmo
NaHCO3
Vph = 0; Vmo > 0
MVmo
NaOH + Na2CO3
Vph > Vmo
NaOH: M(Vph – Vmo)
Na2CO3: MVmo
NaHCO3 + Na2CO3
Vph < Vmo
NaHCO3: M(Vmo – Vph)
Na2CO3: MVph
In this experiment, a sample of soda ash will be analyzed using the double
indicator titration described.
APPARATUS
Iron stands
Burette clamps
CHEMICALS
HCl, concentrated
Soda ash sample
Methyl orange
Phenolphthalein
(2017 Edition)
GLASSWARE
Burettes (50-mL)
Volumetric flasks (250-mL)
Volumetric pipettes (25-mL)
Beakers
Graduated cylinders (100-mL)
Spatulas
EQUIPMENT
Analytical balance
Hotplate
PROCEDURE
NOTE: The use of boiled distilled water is necessary for this experiment. Boil
2.00-L distilled water a day before the experiment. Store this in a sealed
container.
NOTE: Record all data with tolerances. Account these for error propagation. For
error propagation instructions, refer to Appendix 6.
Preparation of Solutions
Prepare the following solution quantitatively using boiled distilled water per
class:
1. 250.0 mL 1.0 M stock HCl solution
NOTE: Use the 3.0 M HCl solution from Solution Preparation experiment
Prepare the following solution quantitatively using boiled distilled water per
group:
1. 250.0 mL 0.0500 M standard HCl solution from 1.0 M HCl
Standardization of 0.0500 M HCl Solution
three flasks, weigh 0.0500 g of the primary standard Na2CO3 to the nearest 0.1 mg.
Record the weights of the primary standard.
2. Add about 75.0 mL of boiled distilled water and swirl to mix and dissolve the
solids.
3. Add 2 to 3 drops of methyl orange indicator. Record the initial burette reading
and titrate with the 0.050 M HCl solution.
4. When the solution just begins to change from yellow to near orange, temporarily
stop the titration and boil the solution to remove the CO2 that was formed. Boil
for 2 to 3 minutes and then cool to room temperature. The solution must be yellow
or near orange at this point. If the solution is red, one has over titrated.
Discard the solution and repeat titration.
5. Resume titration to the endpoint, which is the formation of an orange solution.
Analysis of Soda Ash Sample
1. In a clean Erlenmeyer flask, weigh 0.2500 g of soda ash sample to the nearest
0.2 mg and add 75.00 mL of boiled distilled water. Take three (3) clean and
properly labeled 250-mL Erlenmeyer flasks. Using a volumetric pipette, measure out
25.00 mL of the sample solution into the three flasks. Record the actual weight of
the sample and the total volume of the sample solution.
2. Add about 50.0 mL of boiled distilled water to each flask and swirl to mix.
reading and titrate with the 0.050 M HCl solution.
4. When the phenolphthalein endpoint (first drop of titrant after faint pink
endpoint) is reached, DO NOT refill the burette. Record this volume as the final
volume of acid at the phenolphthalein endpoint and as the initial volume of acid at
the methyl orange endpoint.
5. Add 2 to 3 drops of methyl orange indicator and continue the titration using the
same 0.050 M HCl solution.
2. When the solution just begins to change from yellow to near orange, temporarily
stop titration and boil the solution to remove the CO2 that was formed. Boil for 2
to 3 minutes and then cool to room temperature. The solution must be yellow or near
orange at this point. If the solution is red, one has over titrated so discard the
titration and repeat.
(2017 Edition)
3. Resume titration to the methyl orange endpoint, which is the formation of an
orange solution.
4. Record the final volume of acid at the methyl orange endpoint.
WASTE DISPOSAL
1. Dispose of all titrated solutions into the sink with copious amounts of water.
2. Dispose of excess stock 1.0 M HCl into the acid waste container.
CALCULATIONS:
Determine the:
1. molarity of the standard HCl solution and report it as M ± ΔM
2. percentage composition of the sample and report it as %A ± Δ%A
3. relative standard deviation (in ppt) and confidence limits (95% confidence
level)
GUIDES FOR DISCUSSION
1. Why is the distilled water used in the experiment boiled?
2. Why is a mixture of NaOH and NaHCO3 incompatible?
3. Why the solution needs to be boiled before reaching the methyl orange endpoint?
4. What are the basic components of the unknown soda ash sample based on the volume
relationship at the phenolphthalein and methyl orange endpoints? Report the
percentage of each components and report percent error.
5. What are the possible sources of errors and their effect on the calculated
parameters? Rationalize.
(2017 Edition)
EXPERIMENT 7
Quantitative Determination of Total Hardness in Drinking Water by Complexometric
EDTA Titration
OBJECTIVES
1) apply the concept of complexometric titration in the determination of total
hardness in drinking water.
INTRODUCTION
One of the most common analyses for water, whether it is for domestic (potable) or
industrial (process) use, is total hardness. This parameter is basically associated
to the amount of calcium and magnesium ions in water. Monitoring of this is
important because high amount of calcium and magnesium ions in water will cause
several problems. First, these ions form precipitates with soaps which will lessen
the cleansing action of the soap. Also, hard water would precipitate calcium
carbonate and magnesium carbonate on boiling resulting to clogging of pipes of the
boiler equipment.
The total hardness of water samples is usually determined by complexometric EDTA
titration using Eriochrome Black T (EBT) as indicator and is reported as ppm
calcium carbonate. Using the result in ppm CaCO3, one can classify the hardness of
water based on the table below.
Table 7.1. The water hardness scale.
Water Hardness
ppm CaCO3
Soft
0-20
Moderately soft
20-60
Moderately hard
61-120
Hard
121-180
Very hard
> 180
In this experiment, the amount of calcium and magnesium in water samples will be
determined by titration with ethylenediaminetetraacetic acid (EDTA). The endpoint
takes place when EDTA reacts with the colored metal-indicator complex, thus
breaking the complex. The titration is maintained at pH 10 to allow the Ca-EDTA and
Mg-EDTA complex to form stoichiometrically. The wine-red color of the MgIn- complex
breaks up at the equivalence point as illustrated by the reaction:
H+ + Y4- + MgIn- ↔ MgY2- + HIn2-
wine red blue
(7.1)
APPARATUS
Iron stands
Burette clamps
CHEMICALS
CaCO3, primary standard
Na2H2EDTA●2H2O
MgCl2.6H2O
HCl, concentrated
NH3, concentrated
NaOH
NH4Cl
EBT (1:100:100 / w:w:w /EBT:NaCl:NH2OH.HCl)
GLASSWARE
Volumetric flasks (50-, 100-, 250-, 500-mL)
Volumetric pipettes (5-, 10-, 25-, 50-mL)
Beakers (250, 400-mL)
Burettes (50-mL)
Watch glass
(2017 Edition)
EQUIPMENT
Analytical balance
Top loading balance
Hotplate
pH meter
PROCEDURE
1. 500.0 mL 0.1000 M stock EDTA solution
a. Weigh an appropriate amount of Na2H2EDTA2H2O (FW=372.24) to the nearest 0.1 mg
and transfer to a 400-mL beaker.
b. Add about 200 mL distilled water. Stir to dissolve then add 1.0 g MgCl26H2O
crystals. Mix to dissolve the crystals.
NOTE: The dissolution of Na2H2EDTA∙2H2O may be slow so addition of NaOH pellets
while stirring may be added until the solution is clear. Heating the solution may
also increase the dissolution of Na2H2EDTA∙2H2O.
c. Quantitatively transfer the solution into a 500-mL volumetric flask. Rinse the
beaker thrice with small portions of distilled water and transfer the rinse to the
volumetric flask. Dilute to mark with distilled water, cover and mix.
d. Transfer to a clean and dry reagent bottle. Label as 0.1000 M stock EDTA
solution.
2. 100.0 mL 0.0500 M stock Ca2+ solution
a. Weigh appropriate amount of pure CaCO3 (FW=100.09) to the nearest 0.1 mg into a
250 mL beaker. Add about 40.0 mL distilled water. Take note of the purity of CaCO3
used.
b. Carefully and slowly add concentrated HCl to dissolve the CaCO3 solids while
stirring and heating the solution in a hotplate. Do this until the CaCO3 solids are
completely dissolved or until no more effervescence is observed.
NOTE: The stirring must be vigorous enough to dissolve the solids. It is advisable
to swirl the beaker using a crucible tong instead of using a stirring rod.
c. Quantitatively transfer the solution into a 100-mL volumetric flask. Dilute to
mark with distilled water, cover and mix.
d. Transfer to a clean, plastic (polyethylene) bottle. Label as 0.0500 M stock Ca2+
solution.
3. 250.0 mL 1.0 M NH3-NH4+ pH 10 buffer solution from NH4Cl and NH3
NOTE: Refer to Appendix 3 for the preparation of buffer.
Prepare the following solutions by pair:
1. 250.0 mL 0.0100 M working EDTA solution from 0.1000 M EDTA
2. 50.0 mL 0.0050 M working standard Ca2+ solution from 0.0500 M Ca2+
Standardization of 0.01 M EDTA Solution
1. Pipette 10.00 mL of the 0.0050 M working standard CaCO3 solution into each of
three (3) 250-mL Erlenmeyer flask. Add 75 mL distilled water to each of the flasks.
2. Add 3 mL of buffer solution followed by 2-3 drops of EBT indicator. Swirl to mix
and immediately titrate the solution with the 0.0100 M standard EDTA solution.
NOTE: Avoid adding too much indicator, otherwise the endpoint will not be sharp,
with a gradual color change that is difficult to detect.
(2017 Edition)
3. Record the initial volume of the titrant. Titrate the solution until a change in
color from wine red to a clear blue is observed.
NOTE: Titrate the solution slowly as the endpoint approaches because the color
change is delayed. Over titration may result from rapid titration.
NOTE: The color change may also be observed as from light violet/purple to blue.
4. Record the final volume of the titrant used.
5. Repeat the procedure for the other two trials.
Analysis of Water Sample
1. Using a 50-mL volumetric pipette, measure 50.0 mL of the commercial mineral
water sample into a 250-mL Erlenmeyer flask.
2. Follow steps 2-4 of Standardization.
3. Perform in triplicate.
WASTE DISPOSAL
2. Drain and flush excess solutions into sink with copious amount of water.
(2017 Edition)
EXPERIMENT 8
Quantitative Determination of Dissolved Oxygen Content by Winkler Redox Titration
OBJECTIVES
1) perform the water sampling and pre-treatment techniques for dissolved oxygen
analysis;
2) determine the amount of dissolved oxygen in a water sample from a pond in the
University using Winkler redox titration; and
3) discuss the chemistry behind the Winkler method for dissolved oxygen
determination.
INTRODUCTION
The dissolved oxygen (DO) levels in natural water and wastewater depend on the
physical, chemical and biochemical processes involved in the water system.
Dissolved oxygen determination is a key test for water pollution control and waste
water treatment process control. Table 8.1 shows the water quality guidelines, as
per American Public Health Association, Inc.
Table 8.1. Dissolved oxygen content and water quality relationship.
DO Content* (ppm O2), 20oC
Water Quality
8-9
Clean, good water
6.7-7.9
Slightly polluted
4.5-6.6
Moderately polluted, can sustain life of warm water fishes
Below 4.5
Highly polluted
0-2
Cannot sustain life
*7-11 ppm: ideal for stream fishes including cold water fishes
Winkler method, the classical determination of DO in water is based on an
oxidation-reduction titration process known as iodometric method. The basis of this
method is the oxidizing power or ability of the dissolved oxygen to oxidize the
divalent manganese in the solution. The oxidized Mn is precipitated to hydroxides
of higher valence states (Mn2+ → Mn3+) as Mn(OH)3 with strong alkali. Upon
acidification, the oxidized Mn(III) is reduced to Mn(II) in the presence of iodide
ions with subsequent liberation of iodine equivalent to the DO content of the water
sample.
Several oxidizing and reducing substances, such as dissolved organic matter,
nitrate, nitrite, higher valence manganese compounds, active chlorine, sulfide,
sulfite, ferrous, and ferric, may be present in natural water or wastewater. Due to
the possible presence of these substances, water sampling has been intricately
studied and an accepted technique should be followed before performing DO analysis.
Proper sampling techniques, which include pre-treatment procedures, are performed
to avoid interferences of these substances.
APPARATUS/MATERIALS
Iron stands
Burette clamps
Aluminum foil
CHEMICALS
MnSO4·2H2O
NaOH
NaN3
KI
Na2S2O3·5H2O
Na2CO3
H3PO4
KIO3, primary standard
(2017 Edition)
GLASSWARE
Glass bottle with cap
Watch glass
volumetric flasks (25-, 250-, 500- mL)
Burettes (50-mL)
Syringes (1-mL)
Na2CO3
Beakers (50-, 100-mL)
EQUIPMENT
Analytical balance
Top loading balance
Hotplate
PROCEDURE
1. 25.0 mL 4.0 M MnSO4 from MnSO4·2H2O crystals
a. Weigh the needed amount of crystals in a beaker and dissolve in about 10 mL
distilled water.
b. Filter the solution into a 25-mL volumetric flask and dilute to mark.
2. 25.0 mL 18 M NaOH solution with 5 g KI and 0.15 g NaN3
a. Dissolve the solids in a beaker using approximately 10 mL distilled water while
stirring in a hotplate.
b. Transfer the solution in a 25-mL volumetric flask and dilute to mark.
NOTE: Preparation should be done in a water bath, under the fume hood.
3. 250.0 mL 0.125 M stock Na2S2O3 solution from Na2S2O3·5H2O crystals
a. Weigh the needed amount of crystals in a beaker and dissolve in about 100 mL
boiled distilled water.
b. Transfer the solution in a 250-mL volumetric flask. Wash the beaker
quantitatively with boiled distilled water and catch the washings into the
volumetric flask.
c. Dilute to mark.
NOTE: The stock Na2S2O3 solution must be freshly prepared.
4. 500.0 mL 0.5 M H2SO4 solution
5. Starch solution
a. Weigh 1.0 g of starch in a beaker and dissolve with small amount of distilled
water until a smooth paste is obtained.
b. Pour the paste in approximately 100.0 mL boiled distilled water.
NOTE: The starch solution must be freshly prepared.
NOTE: Keep the solution at 90°C-100°C to avoid drying up of the starch solution.
Add water if necessary.
1. 250 mL 0.0125 M standard Na2S2O3 solution from the 0.125 M stock Na2S2O3
solution
Standardization of Na2S2O3
1. In a 50-mL beaker, weigh 0.15 g of the primary standard KIO3 to the nearest 0.1
mg. Record the weights of the primary standard.
2. Dissolve in about 50 mL of distilled water.
3. Transfer the solution quantitatively into a 100-mL volumetric flask. Dilute to
mark and mix thoroughly.
4. Take three 10.00 mL aliquots and transfer into three 250-mL Erlenmeyer flasks.
5. Add about 20 mL distilled water into each flask.
6. Add 1.0 g KI and 10 mL of 0.5 M H2SO4 to each solution.
7. Immediately titrate the solution with standard Na2S2O3 until a pale yellow color
is obtained.
8. Immediately add 1.0 mL starch solution.
9. Continue titration until the disappearance of the blue color.
10. Perform standardization in triplicate.
(2017 Edition)
Analysis of Water Sample
1. Fill an empty glass bottle covered with aluminum foil to overflowing with the
pond water sample, avoiding the inclusion of air bubbles.
NOTE: The glass bottle should be covered with aluminum foil to prevent exposure of
the water sample to sunlight.
2. Remove the cover slowly and, using syringe, add the following reagents in
succession:
a. 0.5 mL of MnSO4 solution
b. 0.5 mL of NaOH with KI and NaN3 solution
NOTE: Do not allow air bubbles to get in the water sample while the solutions are
added.
3. Close the bottle carefully, avoiding inclusion of air bubbles. Shake the bottle
thoroughly and vigorously. At this point, the solution is filled with precipitates.
4. Remove the cover slowly and add 2.0 mL of concentrated H3PO4 taking care that
the pipette must be just below the surface of the water. The acid will dissolve the
precipitate.
5. Cover and shake the solution and allow it to stand for about 10 minutes.
6. Take a 50.0 mL aliquot of the solution and transfer in a 250 mL Erlenmeyer
flask.
7. Follow steps 7-9 of standardization.
8. Perform sample analysis in triplicate.
9. Express the DO content in the samples in parts per million (ppm).
WASTE DISPOSAL
2. Excess H2SO4, Na2S2O3, and starch solutions may be discarded into the sink with
copious running water.
3. Dispose of excess NaOH with KI and NaN3 into the base waste container.
4. Dispose of excess MnSO4 into the inorganic waste container.
(2017 Edition)
EXPERIMENT 9
Determination of Electrode Potentials
OBJECTIVES
1) relate and apply the concepts of electrochemistry to actual experiments;
2) understand the processes and elements of an electrochemical cell; and
3) determine the spontaneity of redox reactions based on standard reduction
potential.
INTRODUCTION
Reactions in which one or more electrons are transferred are called reduction-
oxidation reactions or redox reactions. Reduction involves gain of electrons while
oxidation involved loss of electrons. For instance, direct transfer of electrons
from Zn atom to each Cu2+ ion occurs when a piece of Zn metal is dropped into a
CuSO4 solution as shown by the equation (9.1).
Zn(s) + Cu2+(aq)→ Cu(s) + Zn2+(aq)
(9.1)
The reaction is spontaneous but no useful electrical work is performed. However, if
the two reactants are separated in such a way that electron transfer is forced
through a wire (Figure 9.1); electrical work can be done by the reaction system.
Such a device is called galvanic or voltaic cell.
Figure 9.1. A simple galvanic cell.
Reaction 9.1 can be split into two half-reactions (9.2 and 9.3) representing two
half-cells:
Zn(s)→ Zn2+(aq) + 2e- (oxidation)
(9.2)
Cu2+(aq) + 2e-→ Cu(s) (reduction)
(9.3)
In Figure 9.1, the two half-cells are connected by a wire with a voltmeter and a
salt bridge. Electrical current flows from the Zn electrode (anode) to the Cu
electrode (cathode) through the voltmeter and the circuit is completed by migration
of ions thru the salt bridge: Na+ toward the cathode and SO42- toward the anode.
Thus, electroneutrality of the two solutions is maintained.
(2017 Edition)
Anodic reaction: Zn → Zn2+ + 2e-
Cathodic reaction: Cu2+ + 2e-→ Cu
Cell reaction: Zn(s) + Cu2+(aq) → Cu(s) + Zn2+(aq)
The Cell Potential, Ecell, and the Standard Cell Potential, E0cell
To conveniently describe a galvanic cell, a shorthand notation, called the cell
notation, is used instead of drawing the complete diagram. In a cell notation, the
components of the cell are written according to the movement of electrons: from
anode to cathode. A single bar indicates a phase boundary while the double bar
represents the salt bridge. Figure 9.1 can be represented by the cell notation:
Zn|Zn2+(1.0 M)|| Cu2+(1.0 M)|Cu
Such cell approximates what is known as standard cell where all substances are at
unit activity. In a galvanic cell, the oxidizing agent pulls electrons from the
reducing agent through the conduction wire. This electron pull or driving force is
called the cell potential (Ecell) or the electromotive force, emf of the cell.
However, at standard conditions, the potential is called the standard cell
potential (E0cell). Ecell is a measure of the tendency for a cell reaction to occur
for the conditions under which the cell operates while E0cell measures the tendency
for the cell reaction to occur when all substances involved are at 1.0 M
concentration.
The dependence of cell potential on concentration results directly from the
dependence of free energy on the concentration which leads to the Nernst equation
(9.4 and 9.5). The Nernst equation gives the relation of the cell potential, Ecell,
to the nature of the electrodes, temperature, and concentration of substances
involved in the cell reaction.
�� =��−2.303��log�
(9.4)
�� =��−��ln�
(9.5)
where R=8.314 J/mol-K; T=temperature in K; n=moles of electrons transferred;
F=96,485 C/mol electrons transferred, and Q= reaction quotient. Solids and pure
solvents are assigned unit activity.
Half-Cell Potential (or single electrode potential)
When a metal M is immersed in a solution of its ions, Mn+, the equilibrium
Mn+(aq) + ne-↔ M(s)
(9.6)
is set up. The tendency of a metal ion to form the metal atom (9.6) differs from
one metal to another. Thus, the potential set up between the metal and its ions
varies from one system to another. The potential of a half-cell is a measure of the
tendency of the half-cell reaction to occur. The greater the reduction potential is
(i.e. the more positive), the greater the tendency for the reduction to occur and
the lower the tendency for the reverse reaction to occur. The more negative the
reduction potential the lower the tendency for the reduction reaction to occur and
the greater the tendency for the reverse reaction (oxidation) to take place
spontaneously. Thus, if two half-cells are connected to form a cell, the half-cell
with greater reduction potential will be the cathode and the one with the lower
reduction potential will be the anode. The cell potential is given by equations
(9.7) and (9.8).
��=��ℎ��−��
(9.7)
��=��ℎ��−��
(9.8)
Standard reduction potentials, E0red, of half-cells are measured relative to the
standard hydrogen half-cell which has standard reduction potential of 0.00V
arbitrarily assigned to it, i.e., for
H+(aq) + e-→ ½ H2(g) E0 = 0.00V
(9.9)
(2017 Edition)
The standard hydrogen half-cell can be replaced by half-cells whose standard
reduction potentials have been measured accurately against the standard hydrogen
electrode.
In the first part of this experiment, standard reduction potentials of various
half-cells will be measured against the Cu2+(1M)/Cu half-cell whose standard
reduction potential is given.
Cu2+(aq) + 2e-→ Cu(s) E0 = +0.34V
(9.10)
In the second part, electrolytic cell will be constructed. Electrolysis involves
forcing a current through a cell to produce a chemical change. This is different
from the galvanic cell wherein the latter converts chemical energy into electrical
energy. Electrolysis will be conducted before measuring the standard reduction
potentials of the halide half-cells. To determine the amount of solid produced
after the electrolysis, the Faraday’s Law (10.11) may be used.
�=��
(9.11)
where m is the mass of the substance liberated at the electrode in grams, Q is the
total electric charge passed through the substance, F is the Faraday’s constant
equal to 96,485 C/mol e-, M is the molar mass of the substance, and z is the number
of electrons transferred per ion. Alternatively, the total electric charge can be
determined from the measured current (I) during the electrolysis multiplied by the
duration (time, t) of the process in seconds. This translates to equation (9.12).
�=��
(9.12)
APPARATUS/MATERIALS
Copper wire
Filter paper
Alligator clips
Zinc stick
Pencil graphite leads
9V or AA batteries
CHEMICALS
KI
FeSO4·7H2O
KBr
H2O2
FeCl3
ZnSO4·7H2O
KNO3
CuSO4·5H2O
GLASSWARE
Beakers (50-mL)
EQUIPMENT
Top loading balance
Magnetic stirrer with spin bar
Multimeter
PROCEDURE
1. 50 mL 1.0 M CuSO4 from CuSO4·5H2O
2. 10 mL 1.0 M ZnSO4 from ZnSO4·7H2O
3. 10 mL 2.0 M FeCl3
4. 10 mL 2.0 M FeSO4 from FeSO4·7H2O
5. 10 mL 1.0 M Fe2+/Fe3+ solution
Pipette 5.0 mL each of 2.00M FeSO4 and 2.00 M FeCl3.
(2017 Edition)
6. 10 mL 1.0 M KBr
7. 10 mL 1.0 M KI
8. 50 mL saturated KCl
Determination of Half-Cell Standard Reduction Potential, E0red
1. Prepare five (5) salt bridges by soaking five (5) filter paper rolls in the
prepared saturated KCl solution.
2. Check if the multimeter and alligator clips are working.
NOTE: To check if the multimeter is working, set the reading to voltage. Then,
connect the positive test probe of the multimeter to the positive pole of the
battery and the negative test probe of the multimeter to the negative pole of the
battery. The display should give a voltage reading. Otherwise, replace the
multimeter.
NOTE: Check if the alligator clips are working by inserting these in the circuit
used in the previous step. Connect the clips to the probes of the multimeter before
connecting to the poles of the battery. Discard and replace clips if the display
does not give a voltage reading.
3. Fill one electrolyte container with 10 mL 1.0 M CuSO4 solution. Fill another
electrolyte container with 10 mL 1.0 M ZnSO4. Prepare the set up as shown in Figure
9.2.
Figure 9.2. Galvanic cell set-up for Zn2+ solution.
4. Set the multimeter in voltmeter. Measure the voltage (Ecell). Note that the
voltmeter should be PARALLEL (Figure 9.2) to the circuit. The positive test probe
of the multimeter is connected to the positive electrode, while the negative test
probe is connected to the negative electrode. A negative voltage reading will only
indicate a reversed attachment to the test probes, but the magnitude remains the
same.
5. Repeat steps 3 and 4 for 1.0 M Fe2+/Fe3+, replacing the Zn2+ solution and use
graphite as the electrode (Figure 9.3). The Cu2+/Cu half-cell and salt bridge must
always be fresh per run.
Figure 9.3. Galvanic cell set-up for Fe2+/Fe3+ solution.
Salt bridge
Zn electrode
(Zn stick)
Zn2+ solution
Cu electrode
(Cu wire)
Cu2+ solution
Salt bridge
Graphite electrode
(Pencil lead)
Fe2+/Fe3+ solution
Cu2+ solution
Cu electrode
(Cu wire)
(2017 Edition)
Electrolytic Cells
1. Fill one electrolyte container with 10 mL 1.0 M KBr solution.
2. Prepare the set-up according to Figure 9.4.
3. Set the multimeter in ammeter. Connect the dry cell and ammeter in SERIES
(Figure 9.4). Connect the positive test probe of the ammeter nearer to the positive
of the power supply, and the negative test probe to the negative pole of the power
supply. Simultaneously turn on the stirrer and start the timer upon connecting the
dry cell. Electrolyze or generate Br2 for 1 minute. Record any observations.
Figure 9.4. Electrolysis set-up for the generation of X2 from KX.
4. Record the current during electrolysis. After the electrolysis, record the exact
time elapsed. Be careful not to disturb the container containing the Br2.
5. Set up another galvanic cell for the electrolyzed solution, as shown in Figure
9.5. Use fresh CuSO4 solution and salt bridge. Measure the voltage (Ecell).
6. Do the same for 1.0 M KI solution.
Figure 9.5. Galvanic cell set-up for the KX/X2 solution.
WASTE DISPOSAL
1. Dispose of all potassium salt solutions into the sink with copious amounts of
water.
2. Dispose of H2O2 in peroxide waste jar.
3. Dispose of all other used and excess reagents into the inorganic waste
container.
For salt bridge (must be covered during electrolysis)
Graphite electrode
(Pencil leads)
Magnetic stirrer
Spin bar
Graphite electrode
(Pencil lead)
KX/X2 solution
Cu electrode
(Cu wire)
Cu2+ solution
Salt bridge
(2017 Edition)
EXPERIMENT 10
Quantitative Determination of the Purity and Dissociation Constant of Potassium
Hydrogen Phthalate by Potentiometric Titration
OBJECTIVES
1) discuss the principles involved in potentiometric titration;
2) detect the equivalence point in a titration curve using this method;
3) determine the purity of KHP; and
4) evaluate the acid dissociation constant of KHP from potentiometric data.
INTRODUCTION
Strong acids completely dissociate in water, but weak acids, like acetic acid, are
only partially dissociated. For a weak monoprotic acid represented by the formula,
HA, partial ionization establishes the following equilibrium:
HA ↔ H+ + A–
(10.1)
and the ionization constant, Ka, is expressed as
��=[�−][�+][��]
(10.2)
Hence,
[�+]=��[��][�−]
(10.3)
At half equivalence point,
[HA] = [A–]
(10.4)
such that [H+] = Ka or pH = pKa.
[H+] = Ka or pH = pKa
(10.5)
In this experiment, the purity and acid dissociation constant of KHP, a weak acid
will be determined using a technique called potentiometric titration.
Potentiometric methods are analytical methods based upon potential measurements.
Direct potentiometric measurements compare the potential developed in a cell
containing the indicator electrode in the analyte solution with the potential
developed when the indicator electrode is immersed in one or more standard
solutions of known analyte concentrations. The determination of pH using a glass
membrane electrode is an example of direct potentiometry.
Potentiometric titration is an example of indirect application of potentiometry.
This method involves measurement of the potential of a suitable indicator electrode
as a function of titrant volume. Potentiometric titrations are generally used to
characterize a newly synthesized organic acid. The equivalent weight and ionization
constant are determined from the following plots.
(2017 Edition)
pH against volume of the titrant
In a plot of pH against volume of the titrant (base), the equivalence point is
shown by a steep rise in the regular curve (Figure 10.1). The pKa corresponds to
the pH when 50% of the acid has been neutralized, or to the pH when half of the
volume, Veq, of the base needed for complete neutralization has been added
(midpoint of the titration, ½ Veq).
Figure 10.1. The regular pH against volume plot.
pH/V against V’ of the titrant
In the first derivative plot (Figure 10.2), the resulting curve gives rise to a
maximum that corresponds to the equivalence point.
Figure 10.2. First derivative plot: pH/V against V’.
2pH/V2 against V’’ of the titrant
In the second derivative plot (Figure 10.3), the resulting curve gives an x-
intercept that corresponds to the volume of titrant needed to reach the equivalence
point. This also coincides to the derivative of the slope of the first derivative
plot, 2pH/V2.
(2017 Edition)
Figure 10.3. Second derivative plot: 2pH/V2 against V”.
V’ and V” are average volumes of the titrant used and are written in the x-axis of
the first and second derivative plots, respectively.
CHEMICALS
NaOH
KHP, primary standard
KHP sample
phenolphthalein
GLASSWARE
Burettes (50-mL)
Beakers (250-mL)
Graduated cylinders (100-mL)
EQUIPMENT
Analytical balance
Top loading balance
pH meter
Magnetic stirrer with spin bar
PROCEDURE
The following solution is prepared by group:
1. 250 mL 0.10 M NaOH
NOTE: Use the 1.0 M NaOH prepared from Solution Preparation experiment.
Standardization of 0.10 M NaOH
three flask, weigh 0.1 g of the primary standard KHP to the nearest 0.1mg. Record
the weights of the primary standard.
2. Add about 50-mL of distilled water and swirl to mix and dissolve the solids.
reading and titrate with 0.10 M NaOH solution until phenolphthalein endpoint.
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Analysis of the KHP Sample
1. Weigh out approximately 0.5 g of the KHP sample to the nearest 0.1 mg into each
of three clean 250-mL beakers.
2. Add 100.0 mL of distilled water into each beaker.
3. Set up the pH meter, magnetic stirrer and base burette according to Figure 10.4.
a. Place a spin bar into the beaker containing the sample solution.
b. Place the beaker on to the magnetic stirrer and assemble the burette in place.
c. Position the electrodes such that the glass bulb is totally immersed into the
solution.
Figure 10.4. The potentiometry setup.
4. Switch on the magnetic stirrer and make sure that the spin bar does not hit the
electrodes. Adjust the electrode’s position if necessary.
5. Record the pH of the solution before starting the titration. Titrate the first
sample solution by adding an increment of 1.0 mL of the base. Record the volume of
the base and the corresponding pH reading after each addition of the titrant.
Approximate the equivalence point by noting the volume at which a large change in
pH occurs.
NOTE: Use a spreadsheet software (e.g., Microsoft Excel) to record potentiometric
titration data. Provide the instructor with the file.
6. For the second and third trials, titrate the solution very carefully:
a. add the base solution using 1.0 mL increment at the beginning
b. at  5.0 mL of the equivalence point, titrate the sample solution using 0.5 mL
increments
c. at  3.0 mL of the equivalence point, titrate the sample solution using 0.2 mL
increments
d. at  2.0 mL of the equivalence point, titrate the sample solution using 0.1 mL
increments.
7. Continue the titration beyond 5.0 mL of the equivalence point using 0.5 mL
increments until pH 11 is reached.
NOTE: Store the excess 0.10 M NaOH in reagent bottle for Ion Exchange
Chromatography experiment.
WASTE DISPOSAL
1. Dispose of all titrated solutions into the sink with copious amount of water.
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EXPERIMENT 11
Quantitative Determination of Copper(II) Concentration by Spectrophotometry
OBJECTIVES
1) apply spectrophotometry in the quantitative analysis of copper (II) solutions;
2) operate a spectrophotometer and measure transmission properties of solutions;
and
3) determine an unknown copper (II) concentration in a sample using Beer’s Law.
INTRODUCTION
Spectrophotometry is an analytical technique in measuring transmission properties
of materials as a function of wavelength. The diagram below shows a radiant energy
with intensity Io directed at a sample solution in a transparent cell or cuvette.
The solution can absorb a portion of this energy and the unabsorbed energy is then
transmitted with intensity I.
Figure 11.1. Diagram of a beam of light as it travels through a sample in a cell of
width l.
The amount of energy absorbed by the solution can be measured in transmittance, T,
or in absorbance, A, where
�=��
(11.1)
and
�=log��=log1�
(11.2)
To determine the relationship of the absorbed energy to a solution’s concentration,
one must apply the Beer’s Law, or more accurately the Beer-Lambert-Bouguer Law,
�=��
(11.3)
where a = absorptivity with units of ppm-1. cm-1, a measure of how well a substance
absorbs light
b = path length with units of cm, the width of the cell or cuvette in which the
sample is contained
c = concentration of the component of interest in the solution with units of ppm
The Beer’s Law gives a convenient linear relationship of the absorbed energy with
the concentration of the absorbing species dispersed in the solution. In this
experiment, Cu(II) solutions of known concentration are prepared and are converted
to [Cu(NH3)4]2+ species by the addition of concentrated ammonia. The absorbed
energies of these solutions are then collected at the pre-determined wavelength of
maximum absorption, max.
This absorbed energy can be detected by means of a spectrophotometer (Figure 11.2).
radiant energy /
radiant energy / light sourcelight source
transmitted energy /
transmitted energy / unabsorbed unabsorbed energyenergy
(2017 Edition)
Figure 11.2. Block diagram illustrating the components of a single-beam UV-Vis
Spectrophotometer.
Furthermore, the various absorbance values of known Cu(II) concentration are
graphed and correlated to determine the unknown concentration of Cu(II) in a
sample.
CHEMICALS
Cu(NO3)2.5H2O
concentrated NH3
GLASSWARE
Beaker (100-mL)
EQUIPMENT
Top loading balance
UV-Vis spectrophotometer
1 cm cuvette
PROCEDURE
1. 250.0 mL standard 2500 ppm Cu(II) stock solution
a. Weigh and dissolve appropriate amount of Cu(NO3)2·5H2O crystals in enough
distilled water.
b. Transfer quantitatively into a 250-mL volumetric flask and dilute to mark.
2. Working standard solutions
a. Pipette 0.00, 2.00, 4.00, 6.00, 8.00, and 10.00 mL of the standard stock
solution of Cu(II) into six different clean 50-mL volumetric flasks.
b. To each flask, add 10 mL of concentrated NH3 solution and dilute to volume with
distilled water. The flask with 0.00 mL of stock solution is the reagent blank.
NOTE: Store excess standard 2500 ppm Cu(II) stock solution in a reagent bottle.
Determination of the Analytical Wavelength
1. Measure the absorbance of the most concentrated working standard Cu(II) solution
against a reagent blank from 300 nm to 700 nm.
NOTE: Refer to Appendix 2 for proper use of UV-Vis spectrophotometer.
2. From the plot of absorbance against wavelength, determine the analytical
wavelength, max, for the analysis.
Preparation of the Calibration Curve
1. Measure the absorbance of the solutions prepared in Part A step 2 at the
analytical wavelength obtained previously.
Determination of the Cu(II) Concentration of the Unknown Solution
1. Obtain a solution of unknown Cu(II) concentration from your instructor.
2. Add 10.0 mL of concentrated NH3 solution and dilute to volume with distilled
water.
3. Measure absorbance readings for the unknown solution trice.
WASTE DISPOSAL
1. Dispose of all excess standards and samples into the inorganic waste container.
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EXPERIMENT 12
Quantitative Determination of Total Ion Concentration by Ion-Exchange
Chromatography
OBJECTIVES
1. discuss the principles behind ion-exchange chromatography and its use as a
technique for separation, and
2. determine the total ion concentration of the sample using the technique.
INTRODUCTION
There are two general types of ion-exchange resins, the cation exchanger and the
anion exchanger. Cation-exchange resins contain acidic functional groups attached
to the aromatic ring of the insoluble organic molecule. Sulfonic acid groups,
-SO3H, make up the active sites on the resin. Dowex 50 is a common and efficient
cation-exchange resin. After HCl treatment, the ionizable RSO3-H+ groups are formed
on the resin. The hydrogen ions exchange with other cations in the following
manner:
n RSO3-H+ + Mn+ → (RSO3)nM + n H+
(12.1)
Anion-exchange resins are composed of hydroxyl ions attached to basic group on the
resin.
n RNH3+OH- + An- → (RNH3)nA + n OH-
(12.2)
Going back to equation (12.1), since the exchange process is fast and complete,
equivalents of displaced protons can readily be determined by titration of the
eluate (solution collected after separation) with standard NaOH. Cation
concentration is calculated from the amount of displaced hydrogen ions.
MATERIALS/APPARATUS
Absorbent cotton
pH paper
Iron stands
Burette clamps
CHEMICALS
NaOH
HCl, concentrated
Dowex 50 cation-exchange resin
Phenolphthalein
GLASSWARE
Burettes (50-mL)
Beakers (100-mL)
Volumetric flasks (100-mL)
Watch glass
PROCEDURE
NOTE: Use the 0.10 M NaOH from Potentiometry experiment.
NOTE: Use the 3.0 M HCl solution from Solution Preparation experiment.
NOTE: A 50-mL burette may be used instead of an ion-exchange column.
NOTE: The resin was already soaked in water and concentrated acid prior to use.
Preparation of the Column
1. Place a wad of absorbent cotton at the bottom of a clean ion-exchange column.
Make sure that it is enough to support the resin without stopping the flow of
liquid.
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NOTE: The cotton should not be very thick for easier removal of the resin and a
more controllable flow rate.
2. Fill up 1/4 of the ion-exchange column with the prepared resin. Gently pour the
resin as it is suspended in concentrated acid solution. Do not allow the level of
liquid to fall below the resin level at any time. Wash the sides of the column once
some of the resin adheres to the sides. Open the column stopper to allow some of
the liquid to flow out of the column.
3. Wash out the excess acid in the column with distilled water until the pH of the
eluate is equal to the pH of the distilled water being used. Check pH using pH
paper. Once pHeluate = pHdistilled water, the column is ready for use.
NOTE: Test the pH of the latest eluate drop (by catching it in a watch glass) and
not the pH of the eluate in the receiving flask.
Determination of the Total Cation Concentration
1. Obtain an unknown sample from your instructor and place it in a 100-mL beaker.
2. Pipette out 10.00 mL of the sample and pour it into the prepared column.
3. Place a 250-mL Erlenmeyer flask under the column as receiver of the eluate. Open
the stopcock until the rate of flow is about 30 drops per minute.
4. Pour the remaining solution into the column while collecting the eluate into the
5. Wash the column with distilled water. Washing is enough when a drop of the
eluate shows a pH equal to that of the pH of the fresh distilled water being used.
6. Combine the washings and the eluate in the same 250-mL Erlenmeyer flask.
7. If the pH of the eluate is already equal to the pH of the distilled water, stop
collecting and titrate the acid solution in the 400-mL beakers with standard 0.1000
M NaOH solution using phenolphthalein as indicator.
NOTE: Test the pH of the latest eluate drop (by catching it in a watch glass) and
not the pH of the eluate in the receiving flask.
8. Perform titration in triplicate.
Storage of Resin
1. Pour 3.0 M HCl solution into the column until the blue color of the resin
disappears and it reverts back to its original yellowish-brown color.
2. To transfer the remaining resin to the original container, invert the burette
and pour the resin with acid to the original container. Repeat this step until all
the resin has been transferred.
WASTE DISPOSAL
1. DO NOT dispose the excess resin. Return the resin to the instructor.
2. Drain all titrated solutions down the sink with copious amount of water.
3. Dispose of used cotton into the solid waste container.
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Appendix 1
Laboratory Guidelines and Techniques in Analytical Chemistry
LABORATORY GUIDELINES
1. All students are required to wear a lab gown and safety goggles during each
experiment. This will be strictly enforced to avoid accidents caused by chemical
spills and other incidents.
2. Shorts, skirts, sandals, slippers are not allowed during experiments.
3. Avoid wearing contact lenses inside the laboratory. It sticks to the eyeball in
the presence of organic solvents.
4. Eating, drinking, smoking, and playing inside the laboratory are strictly
prohibited.
5. All accidents, injuries, breakages and spills, no matter how minor, must be
reported immediately to the instructor.
6. Should a chemical get into your mouth, spit it out and rinse your mouth
thoroughly with water. Similarly, if any chemical comes into contact with any other
parts of your body or clothes, wash thoroughly with plenty of water.
7. Unauthorized experiments are strictly prohibited.
8. Unauthorized person(s) shall not be allowed in a laboratory.
9. The working area must be cleared of unnecessary materials. Put all bags and
books in designated areas.
10. Do not bring reagent bottles to your working area.
11. Avoid wasteful use of reagents, water, and electrical power.
12. Solids, water, and other liquids spilled on your working area must be cleaned
up as soon as possible.
13. Always pour waste reagents into their respective disposal jars (never in the
sink, otherwise stated), as these chemicals cause cumulative damage to our drainage
system.
14. Deposit insoluble wastes such as paper, wood, glass, cork, etc. in the solid
waste bin.
15. First aid kits and fire extinguishers are located in the respective preparation
rooms.
16. Replace the top of every container immediately after removal of reagent.
17. Hold stoppers of reagent bottles between fingers. Never set a stopper on a
desktop.
18. Never return any excess reagent to a bottle, unless specifically directed, to
avoid contamination.
19. Avoid inserting spatulas into a bottle that contains a solid chemical. Instead,
shake the capped bottle vigorously to break up encrustation; then pour out desired
quantity.
20. Procedures involving the liberation of volatile or toxic or flammable materials
shall be performed in a fume hood.
21. Before leaving see to it that:
a) your locker is locked,
b) your assigned working area is clean and dry, and
c) all floating equipment are returned to the instructor.
LABORATORY TECHNIQUES
Cleaning of glassware
1. Cleaning of glassware should be done prior to use.
2. Wash glassware with a detergent solution and then rinse initially with copious
amounts of tap water and, afterwards, with several portions of distilled water.
3. It is not necessary to dry the interior surface of glassware before use. It can
cause contamination.
4. Never use a test tube brush when cleaning volumetric glassware.
5. Always rinse with distilled water after rinsing with copious amounts of tap
water.
6. For pipettes:
a) Draw detergent solution to a level 2 to 3 cm above calibration mark using an
aspirator.
b) Drain solution and then rinse pipet with several portions of tap water.
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c) Fill pipet with distilled water, approximately 1/3 of its capacity and rotate so
that entire interior is wetted. Repeat this process twice.
7. For burettes:
a) Soak in a liquid detergent solution.
b) Drain solution and then rinse with several portions of tap water.
c) Fill burette with distilled water, approximately 1/3 of its capacity and rotate
so that entire interior is wetted. Repeat this process twice.
Quantitative Transfer of Liquids
1. Insert a funnel into the neck of the volumetric flask.
2. Use a stirring rod to direct the flow of liquid from the beaker to the funnel.
3. Rinse both the rod and the beaker with distilled water and transfer the washings
to the volumetric flask.
4. Repeat the rinsing process at least two more times.
Aliquot Measurement
1. Rinse pipet with solution to be used before measuring out aliquot.
2. Forefinger must be faintly moist to facilitate easy control. Too much moisture
makes control impossible.
3. Rinse pipet thoroughly after use.
4. Residual liquid is never blown out of a volumetric pipet or from some measuring
pipets.
Dilution of Solutions
1. Solute should be dissolved completely before diluting to the mark.
2. Bring the liquid level almost to the mark and allow time for drainage.
3. Use a dropper/wash bottle to make final additions of solvent as are necessary.
4. Firmly stopper flask and invert it repeatedly to ensure thorough mixing.
5. Always add concentrated acid to water; never water to acid when diluting acid
solutions.
Filling of Burette
1. Ensure that stopcock is closed.
2. Add 5 to10 mL of the titrant and rotate the burette to wet the interior
completely. Allow the liquid to drain through the tip. Repeat this at least two
more times.
3. Fill the burette until above the zero mark.
4. Free the tip of air bubbles by rapidly rotating the stopcock and permitting
small quantities of the titrant to pass.
5. Lower the level of the liquid just to or somewhat below the zero mark.
6. Do not store base solutions in a burette for a long time, it can cause glass
stopcocks to freeze upon long contact.
Titration
1. Right-handed persons should use their right hand in swirling the flask and left
hand in controlling the stopcock.
2. Ensure that the tip of the burette is well within the titration flask.
3. Introduce the titrant in increments of about 1 mL and swirl constantly to ensure
thorough mixing.
4. Decrease the size of the increments as the titration progresses. Addition should
be dropwise when endpoint is near.
5. Allow for drainage for at least thirty seconds before recording the final
volume.
Reading of Volumes
1. Always read the lower meniscus which is the curved surface of a liquid at its
interface with the atmosphere.
2. Read at eye level to avoid the apparent displacement of a liquid level as an
observer changes position or parallax error. Volume will appear smaller if read
below eye level. Volume will appear larger if read above eye level.
(2017 Edition)
Weighing of Objects
1. Always allow an object that has been heated to return to room temperature before
weighing since it causes apparent weight of object to be low.
2. Use crucible tongs to prevent moisture uptake by dried objects during weighing.
3. Keep laboratory balance clean and neat. Clean up any spillages immediately.
4. Use an analytical balance for weighing solids to the nearest 0.1 mg or 0.0001 g,
particularly in weighing primary standards. The top loading balance can be used for
weighing hygroscopic solids, such as sodium hydroxide and potassium permanganate.
Heating and Drying of Objects
1. Always minimize the possibility of accidental loss of a precipitate during
heating or drying.
2. Never place a heated object on the tabletop; instead, place it on wire gauze.
3. Keep the tongs and forceps used to handle heated objects scrupulously clean. In
particular, do not allow the tips to touch the tabletop.
4. When heating using a burner, always use a non-luminous flame, not more than two
inches high. Do not heat in closed containers. Always turn off the burner or the
hotplate when it is not being used.
5. Calibrated glassware should not be heated.
6. Dried materials are stored in desiccators while they cool in order to minimize
moisture uptake.
Filtration of Precipitate
Three steps are involved in filtering an analytical precipitate: decantation,
washing, and transfer.
1. In decantation, as much supernatant liquid as possible is passed through the
filter while the precipitated solid is kept essentially undisturbed in the beaker
where it was formed. This procedure speeds the overall filtration rate by delaying
the time at which the pores of the filtering medium become clogged with
precipitate.
2. Wash liquid is next added to the beaker and thoroughly mixed with the
precipitate. The solid is allowed to settle and the supernate is again decanted.
Several washings may be required depending on the precipitate. Most washing should
be carried out before the solid is transferred.
3. In the transfer process, the bulk of the precipitate is moved from beaker to
filter by suitably directed streams of wash liquid.
(2017 Edition)
Appendix 2
Instructions on Proper Use of Instruments
ANALYTICAL BALANCE
The analytical balances housed at the UP Diliman Institute of Chemistry (e.g.
Mettler AE 200 Toledo) are high precision weighing instruments. To maintain the
quality performance of the balance, the user must know the proper way of using the
balance.
Figure A2-1. Mettler AE 200 Toledo.
General Guidelines
1. Make sure that the area around the balance is clean and free of objects or
materials not needed for the weighing procedure.
2. The balance pan and the balance floor should be free of any dust or foreign
matter. Protect the pan by using a pan cover. Use camel’s hair brush for cleaning.
Keep the doors of the balance chamber always closed. It should only be opened when
placing or removing the object to be weighed.
3. The balance should be levelled by means of a built-in spirit level before
attempting to do any weighing operation. The balance is equipped with a level
indicator on the floor of the weighing chamber and two adjustable levelling feet at
the rear. Adjust the levelling feet until the bubble appears in the center circle
of the level indicator.
4. The following switches are often seen in analytical balances:
a) ON TARE – turns on the balance if it is off; zeros the balance
b) OFF – turns the balance off
c) MODE – selects weighing units, functions, or options
d) PRINT – sends weight data, statistical data, GLP data to computer or printer
For weighing purposes, one will be using only the ON TARE switch. Please do not
press the other switches.
5. The balance should be allowed at least 20 minutes prior to use for warm up.
Operating Procedures
1. Press ON TARE to re-zero the display.
2. Open the door of the balance chamber and place the object or material to be
weighed on to the pan. Use a pan protector if available.
3. Wait for the stability indicator to appear before recording the weight of the
object or material. The stability indicator is the letter “S” that appears on the
left side of the display window.
4. The full capacity of an analytical balance is 210 g, therefore do not weigh any
object or material that is greater than 210 g or you will destroy the balance. The
bars on the upper right hand side of the display window are the capacity bars.
These bars indicate the percentage of the current weight to the balance capacity.
Weighing by Addition
This is done by first determining the accurate mass of a dried container. Then, the
desired quantity of the sample is added to the vessel and increase in the mass is
taken as the mass of the sample. For example,
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Mass of the beaker, g 20.2563
Mass of the beaker + sample, g 20.7775
Mass of the sample, g 0.5212
1. Addition of the sample into the container is done by the use of a spatula or by
tapping the sample vial such that only small portions are added at one time until
the desired mass is obtained. However, since the analytical balance has a TARE
button, when weighing objects or materials that must be held in a container,
pressing TARE may be done to store the weight of the container in the balance’s
memory.
3. Open the door of the balance chamber and place the empty container to be weighed
on to the pan. Its weight is displayed and the stability indicator also appears.
4. Press ON TARE, the display blanks until stable weight readings are received,
then indicates zero. The container’s weight is stored-in memory.
5. Add material to the container. As the material is added, its net weight is
displayed. When the stability indicator appears, record the weight of the material.
6. Removing the container and material from the pan will cause the balance to
display the container’s weight as a negative number.
7. Press ON TARE to reset the balance to zero.
Weighing by Difference
This technique is especially useful when a series of samples of about similar size
are to be weighed. It requires only (n+1) weighings to obtain n samples, compared
to 2n weighings for the addition method. In contrast to weighing by addition, the
receiving vessels need not be dried. This method is best suited when the sample to
be weighed should be protected from undue exposure to the atmosphere as in the case
of a hygroscopic material.
The weighing bottle containing the sample is weighed accurately and the balance
reading zeroed. Then, an approximate quantity of the sample is transferred into the
receiving flask by tapping the weighing bottle slowly. DO NOT use a spatula. The
weighing bottle with sample is weighed again and the amount of the sample
transferred is checked as a negative value on the balance’s readout. If this is
within the range for the sample size, then the mass is recorded and the process is
repeated for the next sample. If it is too little, the mass is ignored and more of
the sample is added into the receiving flask. Thus, the decrease in mass is taken
as the mass of the sample:
Mass of the vial + sample, g (TARED) 0.0000
Mass of the vial –sample, g -0.1500
Mass of sample drawn, g 0.1500
2. Open the door of the balance chamber, place the sample vial on to the pan and
close. Its weight is displayed and the stability indicator also appears.
3. Press ON TARE, the display blanks until stable weight readings are received,
then indicates zero. The weight of the sample + vial is stored-in memory.
4. Open the door of the balance chamber, take out the sample vial and close.
Carefully tap the vial to add in small amounts of sample onto another container.
5. Open the door of the balance chamber, return the vial and close. The balance
should give a negative reading since a specific amount of sample was taken from the
container. The reading on the balance gives an idea of how much sample was
obtained.
6. If the sample drawn out is enough, then record the weight and press ON TARE to
reset the balance to zero.
7. If the sample drawn is NOT enough, then, follow steps 3 to 6.
8. After weighing, remove all objects or materials from the balance area. Be sure
that the balance pan and chamber are clean. Be sure that the doors of the balance
chamber are closed.
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UV-VIS SPECTROPHOTOMETER
The UV-Vis spectrophotometer to be used for Chemistry 26.1 is Shimadzu UVmini-1240
single beam spectrophotometer, housed at the Analytical Services Laboratory of UP
Diliman Institute of Chemistry.
Figure A2-2. Shimadzu UVmini-1240.
1. Turn on the spectrophotometer.
2. Determine analytical wavelength.
a) Fill up the cuvette with the standard solution with highest concentration (after
rinsing the cuvette properly with distilled water and solution to be measured).
b) Place the cuvette at the cuvette holder. Make sure the clear side faces the
light source.
c) Go to Spectrum Mode.
d) Set the wavelength range.
e) Scan.
f) Obtain peak. This corresponds to the analytical wavelength.
3. Autozero.
a) Fill up the cuvette with blank or reference solution (after rinsing the cuvette
properly with distilled water and solution to be measured).
b) Place the cuvette at the cuvette holder. Make sure the clear side faces the
light source.
c) Press Autozero for background correction.
4. Read absorbance measurements of the standard and sample solutions.
a) Press Go to WL and input the obtained analytical wavelength.
b) Starting from the standard solution with lowest concentration to highest
concentration, fill up the cuvette with the solution to be measured.
c) Place the cuvette at the cuvette holder. Make sure the clear side faces the
light source.
d) Scan each solution.
e) Record the absorbance readings for each solution.
5. After reading all the standard and sample solutions, rinse all cuvettes with
distilled water and allow it to drain. Return the cells in the rack or in their
storage container. Check with your instructor to see whether the instrument is to
be left on for other students; if not, turn it off.
Cleaning and Handling of Cuvettes
1. If the cell is visibly contaminated, it must be cleaned with a warm dilute
detergent solution. If not, then rinse with distilled water. In the analysis of the
sample, rinse the cell at least three times with a small amount of the sample
solution.
2. In most spectrophotometers, radiation passes through the clear (non-frosted)
side of the cell. Therefore, you should handle only the frosted portion of the cell
when filling and rinsing with solution and when placing it into the cell holder.
3. Be sure to wipe off any liquid or smudges on the outside of the cell as much as
possible, including the entire bottom half.
(2017 Edition)
pH METER AND GLASS MEMBRANE ELECTRODE
The pH meters housed at the UP Diliman Institute of Chemistry (e.g. Adwa and
Jenway) are highly sensitive instruments for potentiometric and pH measurements.
Figure A2-3. Jenway pH meter
1. Plug the pH meter into the power supply.
2. Select the pH mode on the function switch. Allow 15-20 minutes warm up.
3. Calibrate the pH meter before use:
a. Rinse the electrode with distilled water from a wash bottle. Gently blot off
excess water with tissue paper. This will minimize carryover and contamination.
b. Immerse the electrode in the pH 7 buffer solution. Allow sufficient time for the
pH reading to stabilize. Set the display to the correct value of the buffer using
the BUFFER control.
c. Rinse the electrode with distilled water and blot dry with tissue paper.
d. Immerse the electrode in pH 4 or 10 buffer (the former if acidic substances will
be measured, the latter if basic solutions). Allow sufficient time for the pH
reading to stabilize. Set the display to the correct value of the buffer using the
SLOPE control.
4. Measure the pH of the sample(s):
a. Rinse the electrode with distilled water and blot dry with tissue paper.
b. Immerse the electrode in the unknown solution. Allow the reading to stabilize.
The display will indicate the value of the solution directly in pH. Note the
reading.
c. Rinse the electrode with distilled water and blot dry with clean tissue prior to
immersing in the next sample.
General Guidelines
1. Rinse the electrode thoroughly after use.
2. Handle the electrodes with care. Do not touch the sensitive glass pH membrane.
Do not rub the electrode as this may induce an electrostatic charge.
3. During use, ensure the electrode is rinsed between each measurement to eliminate
contamination of solutions.
4. Turn off pH meter after use.
(2017 Edition)
Appendix 3
Preparation of Buffer Solutions
100 mL of 0.10 M HOAc-NaOAc buffer solution of pH 4.0 from 1.0 M HOAc and 1.0 M
NaOAc
1. Buffer system:
H2O(l) + HOAc(aq) ↔ OAc-(aq) + H3O+(aq)
2. Calculate the total moles of buffer components based of the given stock
solutions to be used.
Total moles buffer = volume of buffer x conc. of buffer
= moles acid component + moles base component
= (0.100 L)(0.10 M) = 0.0100 mol
3. Using the Henderson-Hasselbalch equation, determine the number of moles of the
acid and the base to be used in preparing the buffer.
��=��+log[��][��]
4.0=4.74+log[��][��]
log[��][��]=−0.74
[��][��]=0.182
(� ��)(� ��)�� (� ��)(� ��)�� =�� =0.182
There are two working equations and two unknowns used to calculate for the moles of
buffer components.
�� =0.182(�� )
�� +�� =0.0100 ��
�� =0.00846 �� =0.00154 ��
4. From the corresponding stock solutions, the volume of acid and base components
can be calculated.
�� 1.0 � ��=0.00846 ��1.0 � ��=0.00846 �=8.46 �� 1.0 � ��=0.00154 ��1.0 �
��=0.00154 �=1.54 ��
5. Pipette out 8.46 mL of 1.0 M HOAc and 1.54 mL of 1.0 M NaOAc.
7. Determine the pH of the solution with a pH meter.
8. Adjust the pH if necessary by the addition of either an acid or base.
(2017 Edition)
100 mL of 0.10 M NH3-NH4Cl buffer solution of pH 10.0
1. Buffer system:
H2O(l) + NH3(aq) ↔ NH4+(aq) + OH-(aq)
2. Calculate the total moles of buffer components based of the given stock
solutions to be used.
Total moles buffer = volume of buffer x conc. of buffer
= moles acid component + moles base component
= (0.100 L)(0.10 M) = 0.0100 mol
3. Using the Henderson-Hasselbalch equation, determine the number of moles of the
acid and the base to be used in preparing the buffer.
��=��+log[��][��]
10.0=9.26+log[��][��]
log[��][��]=0.74
[��][��]=5.495
(� ��)(� ��)�� (� ��)(� ��)�� =�� =5.495
There are two working equations and two unknowns used to calculate for the moles of
buffer components.
�� =5.495(�� )
�� +�� =0.0100 ��
�� =0.00846 �� =0.00154 ��
4. From the corresponding stock solutions, the volume of acid and base components
can be calculated.
�� 3=0.00846 ��14.8 � ��3=0.000572 �=0.572 �� 4��=0.00154 ��(53.49
��)=0.0824 �
5. Weigh out 0.0824 g NH4Cl crystals to the nearest 0.1 mg and add 0.572 mL of
concentrated NH3.
7. Determine the pH of the solution with a pH meter.
8. Adjust the pH if necessary by the addition of either an acid or base.
(2017 Edition)
Appendix 4
Properties of Common Acids, Bases, and Primary Standards
Table A4-1. Properties of common acid and base solutions.
Solution
Formula Mass
Molarity
Normality
Weight Percent
Acetic Acid, CH3COOH
60.0
17.4
17.4
99.8
Ammonia, NH3
17.0
14.8
14.8
25
Formic Acid, HCOOH
46.0
23.4
23.4
90
Hydrochloric Acid, HCl
36.5
12.1
12.1
37
Nitric Acid, HNO3
63.0
15.8
15.8
70
Sulfuric Acid, H2SO4
98.1
18
36
96
Perchloric Acid, HClO4
100.5
11.65
11.65
70
9.2
9.2
60
Phosphoric Acid, H3PO4
97.1
14.8
44.6
85
Potassium Hydroxide, KOH
56.1
13.5
13.5
50
1.94
1.94
10
Sodium Hydroxide, NaOH
40.0
19.1
19.1
50
2.75
2.75
10
Table A4-2. The properties of common primary standard solids.
Solid
Formula Mass
% Purity
Potassium Hydrogen Phthalate, KHP
204.2
99.5
Sodium Carbonate, Na2CO3
106.0
99.5
Potassium Iodate, KIO3
214.0
99.5
Calcium Carbonate, CaCO3
100.1
99.5
(2017 Edition)
Appendix 5
Tolerances of Common Laboratory Glassware and Equipment
Table A5-1. Tolerances of common laboratory glassware and equipment.
Glassware/Equipment
Tolerance
Primary Use
Graduated Cylinders
Measurement of approximate volumes
10 mL
 0.1 mL
25 mL
 0.3 mL
50 mL
 0.4 mL
Measuring Pipettes
Delivery of any volume ranging from
0.1 to 25 mL
2 mL
 0.01 mL
5 mL
 0.02 mL
10 mL
 0.03 mL
25 mL
 0.05 mL
Volumetric Pipettes
Delivery of single and fixed volume between 0.5 and 200 mL
5 mL
 0.01 mL
10 mL
 0.02 mL
25 mL
 0.03 mL
50 mL
 0.05 mL
Burettes
Titrations
50 mL (Class A)
 0.05 mL
50 mL (Class B)
 0.10 mL
Volumetric Flasks
If to contain
If to deliver
Solution preparations
50 mL
 0.05 mL
 0.10 mL
100 mL
 0.08 mL
 0.15 mL
250 mL
 0.12 mL
 0.20 mL
500 mL
 0.20 mL
 0.30 mL
1000 mL
 0.30 mL
 0.50 mL
Analytical Balance
 0.0002 g
Mass measurements
Top Loading Balance
 0.01 g
(2017 Edition)
Appendix 6
Significant Figures and Error Propagation
SIGNIFICANT FIGURES
The number of significant figures in a number consists of all of the certain digits
and the first uncertain digit.
Rules
1. A zero may or may not be significant, depending upon its location in a number. A
zero that is surrounded by other digits is always significant because it is read
directly and with certainty from a scale or instrument readout.
Examples: 2.034 cm 4 significant figures
4.17 g 3 significant figures
4.0017 m 5 significant figures
2. Zeros that locate the decimal point for us are not significant.
Examples: 0.0034 g 2 significant figures
30.26 mL 4 significant figures
0.03026 L 4 significant figures
3. Terminal zeros may or may not be significant.
Examples: 2.0 2 significant figures
2500 mL 2 significant figures
2.5 x 103 mL 2 significant figures
Significant Figures in Numerical Computations
1. Addition and Subtraction:
The answer must follow the number of decimal places of the number with least number
of decimal places.
Examples: 8.9444 + 18.52 = 27.46
3.04 – 0.020 = 3.02
3.06 + 7.319 = 10.38
2. Multiplication and Division
The answer must follow the number of significant figures of the number with least
number of significant figures.
Examples: 8.9  12.01 = 0.74
12.7 x 11.2 = 142
108  7.2 = 2130 = 2.1 x 103
3. Logarithms and Antilogrithms
In a logarithm of a number, keep as many digits to the right of the decimal point
as there as significant figures in the original number.
Examples: log 4.000 x 10-5 = -4.3979
log 1.73 = 0.238046 = 0.238
log 6.022 x 1023 = 23.77960 = 23.7796
In an antilogarithm of a number, keep as many digits as there are digits to the
right of the decimal point in the original number.
Examples: antilog 12.5 = 3 x 1012
antilog -3.47 = 3.4 x 10-4
antilog 0.99 = 9.8
(2017 Edition)
Rounding Numbers
1. In rounding a number ending in 5, always round so that the result ends with an
even number. This eliminates any tendency to round in a set direction.
Examples: 61.555 round to 4 significant figures 61.56
61.565 round to 4 significant figures 61.56
2. Do not round until calculations are complete.
3. It is common practice to carry at least one extra digit throughout a series of
calculations to prevent roundoff error. The extra digit is called a guard digit.
ERROR PROPAGATION
Addition
�±�=(�±�)+(�±�)+(�±�) �=√�2+�2+�2
Subtraction
�±�=(�±�)−(�±�)−(�±�) �=√�2+�2+�2
Multiplication
�±�=(�±�)×(�±�)×(�±�) �=�×√(��)2+(��)2+(��)2
Division
�±�=(�±�)÷(�±�)÷(�±�) �=�×√(��)2+(��)2+(��)2
Exponents
�±�=(�±�)� �=�×�×��
Logarithm
�±�=log10(�±�) �=0.434×��
Antilogarithm
�±�=antilog10(�±�) �=2.303×�×��
(2017 Edition)
Appendix 7
Periodic Table of Elements

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Institute of Chemistry

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