tll

CONTENTS

Page
Preface to the Third Edition
iv
About the Author

F''meword to the Student

vi
LIST OF ACTryITIES viii
Recording Laboratory Data x

General Rules for Use of Balances xii

ACTIVITIES L to 15 1 -77

Appendix 1: Rating scale For Analysis of unknown samples

Based on Percent Error 79

Appendix 2: List of Offenses and Correponding Deductions 80

Appendix 3: Laboratory Orientation Session: Sfudent's and

Instructor's Guide 8t
I

Appendix 4: Course Outline (Lecture) 85

Appendix 5: Author's Curriculum Vitae 89

Appendix 6: Record of Users 9l

Appendix 7: Instructor's Manual Evaluation page 92

I
 PREFACE TO THE THIRD EDITION

This laboratory manual is the crystallization of the author's many years of

experience in teaching the course. Its individual activity had undergone
several tests and revisions before being finally grouped into the First
Edition
of this manual. Furthermore, the sequence of the activities in the first
edition had to be monitored with respect to its synchronization with the
iecfure part of the course.

However, the desire for a better manual had rnade the first edition subject
to further scrutiny, resulting in the Second Edition (1988) of the manual. The
fact that the second edition was relatively better was therefore not unexpected.
ln fact, it has endured the test of time, and has been used in the last L5 years at
:he Departonent of Chemisky of MSU-IIT. S[11, the author recognizes the fact
iirat in every endeavor, there is always room for improvement. With this
relief, the second edition was also subjected to further scrutiny just like its
:redecessor.

Thus, based on the performance, data, and results of the sfudents, each
procedure in the second edition was examined for its
correctness, its clarity
and simplicity, and for the reproducibilily of its results. While most of
the
procedures in the second edition passed these criteria, some had
to be revised
for the Third Edition. Furthermore, sample caictrlations and illustrative
tig-ures, rvhen neede4 have been added. Needless to say,
fiis edition should
be relatively much better. Flowever, although every effort was exerted
to
make this edition what it is today, comnients and suggestions are always
rr'elcome for its further improvement.

Mario Borinaga Capangpangan, ph. D.

iiigan City, Philippines
lune, 2004
 ABOUTTHE AUTHOR

Dr. Mario Borinaga Capangpangan* received his ph.D. d.egree in

@fuonmental analytical chemistry from Drexel University, philadelphia
lkrsylvania, u.s.A., but before thaf his B.s. Chemistry degree, cum laude,
h 1y75 from Mindanao state university, Marawi city, and his M.s. in
hvironmental Science degree in 1981, also from Drexel University. He has
prblished international and tocal papers on analytical method development
fuvolving separation and exkaction methods using chromatography and
rpercritical fluid extraction. He won a Fuibright-Hays sciolarship grant in
[m to pursue his master's degree in the United States t]yough the
Itrilippine-Arnerican Educational Found.ation (PAEF) and the Institute of
herrrational Education (IIE). He is currently a full professor of MSU-Iligan
hitute of Technology, which he has served since L975 in various capacities -
c instructor, coilege secretary, and as Chairman of the Deparhnent of
Chemistry.

Dr. Capangpangan's research interest includes supercritical fluid

qhaction, liquid-liquid and tiquid-solid extractiorg sediment
and suspended
sediment analyses, water and wastewater analyses, hydrophobic organic
comPounds (such as polynuclear aromatic hydrocarbons), monitoring and
fate of pollutants, chromatographic methods, and analytical method
development. He is, interestingly, a dedicated and competitive marathon
runner, and has participated in at least 57 running competitions since Lgg6.

AUTHOR'S AUTHENTICATION
The author's signafure below indicates
that this manual is an authorized copy.

'For more information about the author, please visit his website at this address:
htp: / / sun.msuiit.edu.ph / -marium/ Marium.html
 FORE\fORD TO THE STUDENT

The laboratory activities in this manual are

'sfudent' designed such that you, the
can learn not only the basic techniques of
quantitative chemical
analysis, but equatly importan! how the
theoretical aspects of the course are
put into actual pracfice in the laboratory.
while every effort was exerted to
rnake the activities in this manual
clear and simple, a successful performance
of an activity depends largely on your
ability to execute your work correcgy,
carefully, and systematicarly. It is therefore
necessary for you to read and
understand the entire procedure before
coming to the laboratory.

In perfornning the activities in this manual,

you should be reminded of
the following word's of Hamilton and simpson (euantitative
Chemical
Analysis, 12th Edition, page 20):

"Nothing less than absolute integrity is or can be d.emanded. ,f a

quantitatiae analyst, and any disregard af this principle,
howeuer slight, is as
fatal to success as lqck of chemicsl knou)ledge or inaptitude in manipulation
can possibly be."

"Doctoring" or "manufacfuring" of data

or results, therefore, should
never be attempted. rf, for valid reasons, y<lu need
to change some data
during the performance of an activity, have the n ew d.ata
authenticated by
your inshuctor immediatety. Your inskuctor has
the option to deciare your
results nall and uoid, and give you an automatic
zero for an activity where
"doctoring" is evident.

In calculating your results, it is expected that your calculated

results agree
with your obtained data. If a calcutrated result does not agree
with the
corresPonding dat4 then your calculation is erroneous, 'J.0%
and a deduction
for each effoneous result is given, after which you will be asked
to recalculate.

The ratings that you will obtain in the activities in

this manual will be
based on percentage error. Appendix I shows
the corresponding rating at a
certain range of percentage error. This rating scale is
used only in activities
 vii

involving the analysis of unknown samples. However, there are activities

whose ratings are indicated only as "ok" if successfully finished.
These are
the activities which are either inboductory works or activities done
in
:renaration of the analysis of an unknown sample. Examples of such
acijvities are those involving the preparatian of solutions, aalumetric
ratio
:etermination, and standardization.

Finally, but equally irnportant, yor should be reminded of the proper

behaviors" and safety rneasures during and after laboratory activities.
Failure to comply with rules for a smooth and safe conduct of
the activity will
re penalized with deductions, as listed as in Appendix 2. These include
a:nong others the wearing of laboratory gowns, maintaining
a clean work
:iace, thlowing of waste papers into waste boxes and, nof into the
sink, or
careful handling of glasswares to avoid breakage. Before leaving
the
laboratory, you should make it a habit to see to it that the gas
outlets are
c-losed, or that the oven or furnace is unplugged.
After all, a successful
performance of an activi$ done in accordance
with the proper behaviors and
sa-fety measures is the one which should really make
your day!
 LISTOF ACIVINES

Activity TITLE Page Instructorrs Rating

No. Comments

1 Exercise on Weighing Using the 1

Analytical Balance

2 Statistical Evaluation of Weighing 9

Data

3 Gravimetric Determination of 11.

Sulfur in a Soluble Sulfate

4 Determinaticn of the Volumetric 22

Ratio of Hydrochloric Acid and
Sodium Hydroxide Solutions

5 Standardizatio.n of Sodium 30
Hydroxide Against Potassium Acid
Phthalate (KHP)

6 Determination of the Total 34

Alkaline Shength of an Impure
Alkali Carbonate

7 Determination of Acetic Acid 38

Content of Commercial Vinegar

8 Determination of the Volumetric 43

Ratio of Potassium Permanganate
and Ferrous Sulfate Solutions
 ix

Standardization of Potassium
Permanganate Solution Against
Sodium Oxalate

10 Determination of Iron in a Ferric

Chloride Solution by permanganate
Titration

11 Determination of Manganese in
Pyrolusite

12 Determination of the Volumetric

Ratio of Iodine and Thiosulfate
Solutions

13 Standardization of Iodine Solution

Against Arsenic Oxide

Iodometric Determination of
Copper in Copper Oxide

Determination of Chlorine in a
Soluble Chloride

The student should copy the above table af

the List of I,ctivities, in the
format, anto his labsratory Data Notebook. Page numbers in the Data
should be the actual page number, nat the page
numbers listed
 RTCORDINC LABOMTORY DATA

There are three main requirements for the recording

of data obtained 1n
ie analytical laboratory. These may be briefly expressed
as foliows:

The record
(1) should be complete
(2) should be intelligible to any reasonabiy
connpetent chemisf and
(3) should be easy to find on short notice.

These requirements mav be met by adherence

to the following rules.

The sfudent should have a bound. noteboclk for recording

his laboratory
data, calculations, results, and all other rnatters pertinent
to the analysis
of a sample. The pages of the notebook should be numbered,
and a tabre
of contents should. be developed so that any given experiment
can be
quickly found. r

: AII data obtained in the laboratory should be recorded directly

in the
notebook at the time the work is performed. Especially
forbiddenis the
recording of data on loose pqper with. the idea o{ copying
it into the
notebook later. Whiie neahress may be sacrificed somewhat
by ta1:ing the
notebook directly into the laboratory, the prevention of
loss of data and
errors in hanscribing them more than counterbalances this.

Entries should be recorded in ink. If a mistake is made and

a recorded
value is invalidated, it is not to be erased, but is crossed
aut (e.g.,eressed
er+t) so as to be still legible. A notation as to why it
is rejected is made in
the notebook, and should be authenticated immediately
by the insfouctor.

The data in the notebook should be organized and recorded

in a
systematic way. This benefits the student because it is
then relatively easy
to locate errors in the analytical calculations; the sfudent may
thus be
saved repeating an entire determination in order to obtain
satisfactory
results. To facilitate an orderly presentafon of the dat4 the student
should plan how best to record it before the experirnent is acfually
begun.
 xi

It is especially helpful to arrange beforehand a table in which the

experimental data the calculations, and the final results can be entered
systematically.

5 The rules regarding significant figures should be followed in recording

data in the notebook and in calculating the results.

kfcrence;
f,lry, R A. Ir. and underwood A. L., Laboratary Manuar: euantitatiue
Analysis, 6th Edition, Prentice-F{all, Inc., New Jersey (lggr), pp. zs-29.
 xll

GENERAL RULES FOR THE USE OF BALANCES

fflowing points should be noted about the use of any analytical balance:

Tlre balance should be kept clean. Remove dust from the pan
or pans and
ftom the floor of the balance with a camel-hair brush before starting a
reighing.

I"earn the capacity of your balance and never weigh an object

heavier than
lhis am6unf.

The object to be weighed shourd be at the same temperature as the

bnlance' It is preferable not to handle the object with the fingers, and glass
oqecb should not be rubbed with a dry cloth prior to weighing. A
reighing bottle can be handled (but not rubbed) with a clean cloth or a
chip of paper folded around it.

clrerricals should not be placed directiy on the metal pan but should be
r

weighed in weighing bottles. The desired quantity of sample is poured

ant into a suitable container and the bottle re-weighed. The difference in
tire two weights is the weight of sample taken from the bottle.

At the completion of weighing make a final check to make sure that

h) the weight is recorded in your notebook" (b) the balance is clean, (c)
m objects have been left on the pans, (d) the beam and pans have been
urested, and (e) the dust cover has been replaced.

tr the balance does not behave properly, report this fact to the instructor.

ffirence:
R A- Jr. and underwood, A. L., Laboratory Manual:
euantitatiae
Analysis, 6th Edition, prentice-Hail, Inc., New ]ersey (1ggr), p. s6z.
 Sctioity Nb. 1

EXERCISE ON WEICHINC
(Using A Single-Pan Electronic Analytical Balance)

-'\-eighing
is a necessary process in any quantitative chemical analysis.
,:'*:cut the necessary skill in
the weighing process, the results of a
;*::lStative chemical analysis may be considerably erroneous. This exercise
i*:'s lo train the sfudent on the prclce$s of weighing while introducing him
1": :ertain methods of weighing using a single-pan electronic
analytical

-'he analytical balance is a precision instrument,

capable of detecting the
h, q ght of an object of 100
g to within 10.0001 g (r0.1 mg). This is an
;';ertainty of only 1" per rnillion. Until the 1950s, most of these balances
"" *etluo-panbalartces, also referred to as equal-armbalances (Figure
1). Then
3: jtngte-pan, or unequal-arm (sometimes calied constant-load), balance
FtEure 2) essentially replaced the two-pan balance. Today, the
electronic
a:'rie-pan balance (also called the electromagnetic force balance) (Figure
3) is
-::o-lv replacing the mechanical single_pan balance.

It should be emphasized that before this exercise is done, the instructor

';-':u-ld first orient the sfudents with the proper operation of the elechonic
ri'r'tcal balance, and give each sfudent at least a hands-on experience or
:racoce (of an entire weighing process) under the instructor's
direct
s;pervision' A preliminary data table for the practice weighing
is provided in
r:€ &flsw€r sheet for thi.s purpose.

: -TOCEDIIRE:
*-':e' Before doing the following praceilure, make- sure you haae,passed
r-:irss as inilicated by your instructor's approaal -iiit,weighing
the practice
--as*:sr sheet' Your,balanee priority nuiber will-be.sigroiurc in thi pretiminiry in your
decided by your instruitoi, and wiII be
;';;:e!ed (as AL, 81, 42,-82, etc. corrisponding to Balance A snd'Bilanee
B) on the Front cooer
:" i.u/ Answer Notebaok.)
 l" Direct Weighing

iVeigh the following objects and record the corresponding weight

in
lable 1 of your answer sheet. Remember to avoid holding the objects to be
-,reighed with your bare hands.
use tong, forceps, or paper to hoid these
-:lects' When reading the weights, make sure the balance door is ciosed!
--::er rveighing the last object, put the balance "oFF", ready for the next
user.

a) 50-rni beaker (marked "A")

'p) 50-ml erlenmeyer
flask (rnarked "8")
cl porceiain crucible, no cover (marked "C")

g lYeighing By Addirion

\feigh a clean and dry watch grass. (Remember to use tong, forceps, or
:::er to hold the watch glass). Record its rveight in Table 2 (balance door
::sedl). Then with the balance stili in the "oN" position, slowly open the
::,al.-ce door, and carefuliy add a srnall amount of salt (NaCl, refined)
from a
r.:"ria (around half-teaspoon) into the watch glass on the pan. Then close
::*< the balance door. Record the new weight in Table 2, Remove the watch
::-;. containing the salt and transfer the salt from the watch glass into a
: -:-rainer provided fqr used salt. Finally, put the
balance "oFF", ready for the
-:tl US€f,

C lVeighing To A Desired Amount

\\'eigh a clean and dry watch glass. (wipe dry with tissue
paper before
."' sghing, if necessary.
Remember to use tong, forceps, or paper to hold the
' a:ch glass). Record the weight (baiance door ciosedr) of
'' the watch grass in
- mle 3 ' Then with the watch glass still on the pan,
fill up the last two blanks
- lable 3 using 0.2000 gram as the clesired weight of salt to be added into
the
'-' aiCh glass'
Using the last information in Table 3 (weight of watch glass +
.-",-tj, and with the balance in the "oN" positiory
open the balance door and
::c salt in small amounts using a spatula into the watch glass on the pan,
::lcl the new reading (with balance door closedl) coruesponds to the addition
:: exactly 0.2000 gram of sait (i.e., the nerv reading is equal to the weight
of
 3

'"'-atch glass + salt

in Table 3). Then remove the watch glass with salt and put
:lre balance "OFF", ready for the next user. Carefully transfer
the weighed salt
a
-:":o clean piece of paper provided by your instructor. wrap carefully and
:::{v. Label the rvrapped sample as "procedure 3,', with your narne below i!
r: =;bmit it to your instructor.

:" 1\ eighing By Difference

' obtain 3 pieces of 11 -size mimeo paper frorn your insfuuctor. Fold each
:o form a paper container. (Refer to your instructor for demonshation).
-\fark as #1, #2, #9.

Then obtain a weighing botile filled with salt, and weigh. Record the
-'reight (balance door closed!)
in space (a) of rable 4. (Nofe: Throughout
:irc weighing process, handle the rneighing bottte only with a paper
loop
:- strip, as shown in Figure 4; moistwre from the fingers will change the
^ eight of the bottle and cause errors.\

Then with the balance in the "oN" positiory open the balance door and
:arefuI1y remove the weighing bottle from the pan.

; sing a spatula, slowly and carefuily withdraw from the weighing bottle
a:ound a pinch .f
salt (or half-teaspoon) and. directly kansfer this (keep
-,'our hands steady!)
to paper container #1 without any waste. (To make
:he transfer process easier, posi$on the paper container as close as
possible to the weighing bottle.
41fip, do4't repurn a4y BrnpFnf tp ffre
:offle; apd don't bother at this point to caiculate thp weig|rf
of sugap you
nave withdrawn.)

Put the weighing bottle back to the pan, close the balance door, and
record the weight in space (b) of Table 4"

Then with the balance still in the "oN" position, open the balance
door
again and carefuliy remove the weighing bottle from the pan,
 aA

1"ll;:, slowiy and carefully withdraw from the bottle

around a pinch of
:..'i (or half-teaspoon) and directly kansfer this to paper container #2
:,rl-lOUt any nraSte"

l-:i the weighing bottle back to the pan, close the balance door, and
:-cord the weight in space (c) of Table 4.

l:,en with the balance still in the i'ON" position, open the balance door
:iain and carefully remove the bottie from the pan.

-:gain, slowly and carefully withdraw from the

bottle around a pinch of
;.,r: {or half-teaspoon) and directiy transfer this to paper container #3
',"--::.out any waste.

--.:: ihe weighing bottle back to the pan, close the balance door, and
:=.-::i the -weight in space (d) of Table 4.

:::c'for the next user. Then wrap ihe third sugar salt sampie (#3) and
':ei as "Procedure 4", with your narne below it, and. submit to your
-:.s:uctor.

-:i.lr,, calculate the weight of each of the sugar samples from the
;,,-eight data gathered and fill up the remaining
blanks (spaces x, y, z) in
Iable 4.

f.ererences:
)ay, R'A. and underwood, A. L., Laboratory Manual:
euantitatiae Analysis,
Sixth Edition, Prenctice-I:lall, Inc., Ner,v Jersey (L99I), pp. J2-J9.

Fitz, ].s' and schenk, Jr. G.s., euantitative Analytical Chemistry, 3rd Edition,
AIIyn anC Bacon, Inc., Boston (1974), p.542.

Hamilton, L" F. and simpsoru s. G, euantitatiae Chemical Analysis, L1th

Edition, The Macmillan Compan|, New york.(l70), p. 357.
 "-,ot y'"

rrgure 1' Two-pan or equar-arrn anary[car baiance,

rider type.
A: graduated beam; B: rider; C: rider carrier;
D: knife-edge supports; E: zero_point
adjustment screws; F; balance column;
G: pointer; H: sensitivity adjustment weighg
I: balance pans; J: pointer scale; K: pan
supports (Hamilton and simpso n, p.47).

Optical

Counterweight

Weigh pan

Figure 2. A modem single-pan mechanical analytical balance.

(Day and Underwood, p,ZS\
 Eiectromagnetic
force cell

Weigh pan
Digital readout

Figure 3. The eleckomagnetic force analytical balance cell in a classical

enclosure.
(Day and Underwood, p.39)

Figure 4. Handling a weighing bottle with a paper loop.

(Fritz and Schenh p.S42)
 Actiaity No. 1

EXERCISE ON \YEICHINC
(Using A Singte-Pan Analytical Balance)

Ettot, %

Rating, %

Deductions, %:

Net Rating /o =

IIATA AND RESULTS:

hliminary Table: practice Weighing (with Instructor's Direct Supervision)

nitht of object (eg., ball pen, bottle cap, etc.)

g
Instructor's Approval Signature:

frtc: The instructor must observe each indiuidual student from start to
finish of the practice
puuing oN and.orr iy tie-bnrance. rf'the taiishing process
*:t-tr::i:,":;:::!:!::the
p rlonerlv,,the instru.cio., afiiret-ipprooal signatuie in the"niorr"roiii.*3;;';f*ir;:;;Z
ry' .k asked to repeat the-weighii! process until the instructar is satisfied with the
t*nt's performance.)

1. Direct Weighing

weigh! of A (50-ml beaker, empty)

g
weight of B (50-ml erleruneyer flask" empty)
g
weight of C (porcelain crucible without cover, empty)........ 0
ct
 Table 2" Weighing By Addition

iveight of rn'atch glass, empty

rveight of watch glass + salt
n'eight of salt

Table 3. Weighing To A Desired Amount

.se'r,-gkll\stsl\&$xss,ssq\
-,ierg'n\ o\ silt\desrred
amount)
r','eight of watch glass + salt.......

fable 4. Weighing By Difference

Paper Container No.

--::grnal weight of bottie

and salt a)_ g b) _-g c)- g
rew weight of bottle
and salt b)_---*. e c)- g d)_- e
: e t weight of salt sample
taken x)_ g v)s
J' - O z)_g
 Actiuity No. 2

STATISTICAL EVALUATION OF WEIGHINC DATA

This experiment illustrates the use of statistics in evaluating the

r-arufacture of new coins. Ten coins will be used for each of the following
:crominations: one peso, fifty ceniavos, and twenty-five centavos. Each
of
r€tr grouPs of coins will thus constifute a representative sample of coins
rmr6 :',' a particular machine.

The ten coins in each group will each be weighed separately, and
the
'w"'eghts are used to calculate the mean weight, i. This will give an estimate
:r ,, the true mean weight of ali the coins made by the particular machine
:- nng one manufacturing "run". To give an idea of the machine's precision,
ine ;eviations from the mean of each weighing wili also be calculated. In
an*:on, other important statistical parameters will also be determined.

]I.OCEDURE:

- Obtain the ten coins of the group to be weighed and arranged them in
'.heir proper sequence.

balance carefully.
Remember that all the weights obtained are absolute; emors do
not cancel
out as they do in weighing by difference.

Starting with coin no. L, weigh each coin in the group to the nearest
0.0001 & and record each weight directly in your notebook.
To avoid
errors due to moisture, pick the coin with a pair of forceps; do not touch
or hold the coins with your bare fingers.

4. When all the ten coins in the group have been weighed, calculate the
different statistical parameters specified in your data sheet.

R eference:
Fritz, ]. S. and Schenk, G. H., Quantitatiae Analytical Chemistry, Brd. Edition,
Allyn and BacorL Inc., Boston (1974), pp. 534-535.
 1.0

Actiuity No. 2

STATISTICAL EVALUATION OF \(/EICHINC DATA

Ertor, /a
Rating, %

Deductions, %

Net Rating, /o =

].{TA AND RESULTS:

Weights
Coin No. P 1.00-Coin P 0.50-Coin P 0.25-Coin
1

2
3
4
5
6
n

8
9
1n
IU

Statistical Evaluation of Results:

\{ean, *
l"Iedian, M
i:d. Deviation, s
Rel. Std. Dev., %I<SD
:td. Dev. of the Mean, S
i5% Con-fidence Limit o{ *n
REPORTED VALUE

'-\t95% ProbabilityLevel, t=2.228for10degreesof freedofil;t= 2.262forgdegreesof

freedom.
 11

Acttaittt No. 3

CMVIMETRIC DETERIVIINATION oF SULFUR.

IN A SOLUBLE SULFATE

The gravimebic determination of sulfur in a soluble sulfate (such

as
;3 : : sulfate) can be carried out by precipitating the sulfate as barium
sulfate,
: asoi' using BaCl2 reagent. The precipitate is then filtered,
ignited, and
" ::qied to constant weight. From the weight of Basoa the amount of sulfur
; :rl'culated using the appropriate grarsimetric
factor.

The chemical equation for the precipitation reaction is

SO+= (aq) + BaCl2(aq) BaSOa(s) + 2Ct-(aq)
-+
Barium sulfate precipitates as a crystalline solid and conditions
must be
;'"':sted in order to obtain particles as large as possible and to minimize
::::ecipitation. The precipitation is carried. out by rapid mixing of ditute
'.:';aons under conditions of increased solubilify. The solubility is increased
:-, :aising the temperafure and by using an acidic soluton. The precipitate
is
:::i digested at an elevated temperature for I to z hours. when the
::eipitation is carried out in this manner, the particles of precipitate are
.-::ger and purer than otherwise would be obtained.

.:R,OCEDURE:

-.4,. Preparation of Desiccator For Use

Obtain a desiccator {Figure 5) and clean it if necessary. If

its desiccant
is already moist, remove it from the desiccator
and dry in the oven for 1
hour at 1L0-120oC. Then place the dried desiccant back in the
desiccator,
making sure th.e desiccator is tightly closed (air-tight). If necess
ary, appLy a
rnoderate amount of grease on the ground portion of
the desiccator cover
for lubricatiorl for easy opening or closing of the desiccator.
Ask help
from the laboratory technician on this matter.
 T2

B. Furnace Assignment and Orientation

Ask your instructor which furnace is assigned for your use.

The
laboratory technician wili then orient the entire class on the
proper use of
the furnace.

C Weighing-To-Constant-Weight of Empty Crucibles

Using a pencii, iabel three thoroughly-cleaned porcelain crucibles

correspondingly as L, 2, and 3. you may also write your name
or initials
on the crucibles for identification. Heat the three crucibles in
a furnace
at 500oC for t hour. cool in a desiccator for 1.5 minutes;
however, alrow
iaf so that a partial vacuum will
not form in the desiccator after the air inside has cooled. Then weigh
the
crucibles (without the cover). Repeat the heating-cooling_weighing
erocess until successive weighings agree within 0.0004 g (unless
directed
otherwise by the instructor). Filr up the timing tabre in your data
notebook (Table t). Record the weights obtained in Table 2. (Note:
To
aaoid bias in the abtained uteights, caaer the preaious weights
,f the
:rucible while taking the next weightl!!).

n. Drying of Sample

Obtain your sample from your instructor and dry on a watch glass
in
an oven at 11'0-120oC for L hour. Place the dried sample in
an air-tight
'".-eighing bottle
or container. (A Fuji fikn container can be used). store
:n a desiccator. Alternativelp the sample will be provided to you pre_
ciried already, contained in a weighing bottle, ready for part E.

F Determination of Sulfur

; lr:eigh out accurately by the

@ kiplicate samples
previously dried) of between 0.20xx to 0.25xx g each (where x could be any
number) into 800-mL beakers iabeled '1.,2, and.3 respectively. Record your
-'t-eights directly in
the corresponding spaces of lines (a) and (b) of Table 6.
 13

I Add 5 mL of 6 N HCl, and dilute with distilled water to about

b00 mL.

Calculate the volume of 0.1 M BaCl2 reagent (precipitant)

theoretically
required to precipitate the sulfate in the sample (assuming
10% sulfur in
tire sample). Do your caiculations on the left side of your
notebook. Fill
up Table 3 with your results, and present these to your instructor
for
cirecking. (Nofe: For your canuenience, the second column of
Table B
sirotus results of sample c*Iculations, based on a sample
weight af 0.362g
:r)
-l'/

{ \ow heat separately both the sample solution and the solution of BaCl2
ithe calculated volume, with 20 mL excess, contained
in a 50-mL beaker)
nearly tei boiling. Pour the hot BaClz solution
into
ihe hot sample solution and stir vigorousry for a few minutes.
Coiorr,r"
:o heat (but stop stirring this time) until the precipitate has become
:rvstalline and the supernatant liquid is clear. Allow the precipitate
to
setile (by removing from the heat), and test the supernatant liquid for
completeness of precipitation by adding a few more drops of
the BaCl2
'olution. If precipitation is complete the liquid should remain clear.

\ofe: Before proceeding to Procedure 5, Iearn first how to fold a filter

taper properly, as shown in Figure 6.

r Filter the Baso4 precipitate through LL-cm ashless paper (Figure 7

and
Figure 8) and wash with hot distiled water, first by decantation
and
snrbsequently on the filter until free from chlorides. Transfer
the fiiter
and precipitate (tightly folded) to a previously weighed (to constant
ireight) porcelain crucible, and place in the oven at 1L0-120oC
until the
:lter paper becomes dry.

-\ofe: Before proceeding to procedure 6 to char the

fiIter paper, refer first
io Figure 9 for the proper set-up and positian of crucible and coT)er during
the charring process. Then present your set-up to your instructor
for
avproval.
 L4

Remove the crucible containing the dried firter paper

from the oven and
char the filter paper by smoking off over a rozu flame of a
bunsen burner
(Figure 9). Transfer the crucible to a furnace
at 500oC and heat for i. hour.
Cool for L5 rninutes in a desiccator, and weigh. Record the
weight in
Table 5' Repeat the heating-cooling-weighing proce$s
until successive
rveighings agree within 0.0004 g, using the time intervals
indicated in
Table 4, and recording the weights obtained in Table 5. (Nofe:
To auoid
bus in the obtained raeights, coaer the preaious weights of the crucible
while taking the next weight!!!).

trVhen constant rn'eight is obtained, complete the

information required in
Table 6.

Finally, do a statistical evaluation of your results for the percentage

of
-.ulfur in the sample.

tgjt,ences:

Ear " R.A. and underwood, A. L., Laboratory Manual:

euantitatiue Analysis,
sixth Edition, Prenctice-Harl, Inc., New Jersey (1.ggr), p. 1L0.

F{r*'riitory L. F. and Simpsorb S. G.,

Quantitatiue Chemical Analysis, l}th
Edi[on, The Macmillan Company, New York (I97A), p.3SV.
 1"5

Iigure 5. A typical desiccator containing crucibles.

(Day and Underwood, p.5)

@ure 6. Folding a filter plper for collection of precipitate.

Filter paper is normally folded so as to providi
a space between the paper and the
tunnel, excepr ar the top th9 paper, which rh"rle;;;nr;ty ;;;"";turr,
shown above' The second9ffolcl is made so that the u,
enas fail to match by about j./g
inch' Then the paper.is opened into a cone. The
corner of the outside iold on the
thicker side is torn off inbrder.to fit the p"p;;
break up-possible air passage down the iori
ilth" funnel more easily and to
to tr.." r""..i^ ilh ii" paper
cone herd in place in the funner, distiled "u*tis poured in.
applied cautiously to prevent tearing the lvate{
A clean finger,
fragile-riet paper is used to smooth the
paper and obtain a tight seal of papel to glasi
at the top. Air does not enter the
liquid channel with.a property fittea padlr, una ,nnr tn"
of the funnel establislies i g"nue ru.iiot which facilitates
arul*g"-rio,ii tt. utur'
filtration. A
malfunctioning filter can seiiously delay an analysis;
it is preierable ufrar to
reject such filter and prepare a new or,u (D"y and'underwood,
pp" r+_i6l
Figure 7. Technique of filkation
with filter paper.

- sually a precipitate is washed, either with

;;suiled water or a specified wash solution.
l:e washing is generally carried out in
:-nu;rctionwiththe filtration step, as shown
r Flgure 7. It is usually preferable to wash
tt: :recipitate by decantation, at least in
:ses n'here the precipitate seitles rapidly
rrn suspension. The supernatant mother
tr,i':,..,; is carefully poured off through
the
Sr":e: *'hile as much of the precipitate as
mcs;ble is retained in the (continue below)

Figure 8. Use of wash bottle in

transferring precipitate.

beaker. The precipitate is then stirred in

the
beaker with distilled water or wash solutiory
and the washings are decanted through
the
filter. This washing is repeated as often as
desired, until, in the final instance, the
precipitate is not allowed to settle but is
poured into the filter along with the wash
solution. Residues of precipitate remaining in
the beaker are usually transfemed to the
filter by,a directed jet from a wash bottle as
shown in Figure I (Day and Underwood, pp.
15-17).
 L7

Egure 5. l_*, c,her"ring the filter paper with preopitate.

Note"Fthat{9r
in the above set up, the covered c.ucidle is placed
in a clay or silica tria.nglq the crucible cover is in a slanted position
set ajar to permit access of air. The
charring"pr:::: the-n begun with a moderate size of
smoulder, but must l: not flame. The paper should
burn off with a flame. u tnu p"p"r bursts into flame,
the crucible immediateiy to extinguish it. ou.i"i cover
materials
in" .r."r.i.;;b organic
from the paper, collecting on the crucible cover. This
burned off-distills
later at a higher temperature @a! and underwood,
can be
p. 1g).
 18

Activity No. 3

CRAVIMETRIC DETERMINATION OF SULFUR

IN A SOLUBLE SULFATE

Erro\ %

Rating, %

Deductions, %

Net Rating, /o =

-ATA AND RESULTS:

Trble 1: Timing Table (weighing-To-constant-weight of Empty Crucibles)

HEATING COOLING
f CLE Time Start Stop Time Start Stop
\o. Needed IrJeeded
1 60 min 15 min
2 30 min 15 min
3 30 min 15 min
1 30 min L5 min
30 min 15 min
; 30 min L5 min

-
Teble2: weighing-To-constant-weight Data (Empfy crucibles)

lVei
1

2
3
 19

Constant Weight

Table 3: Calculations for the Required Volume of 0.1 M BaCl2 to precipitate

the Sulfate (Assuming I0/" Sulfur in the Sample)

Example* I I tr

+arns of sanple 0.3628

ra:ns of S (sulfur)............ 0.03628 _-:-_
raxns of 8aC12... 0.2357
:oies of BaClz.. 0.001132
::-i- of 0.1. M B.aC'i12............. 17.32
:I- of 0.1 M BaCl2plus
f- rnl- excess....... 31.32

*l"[clar weights
needed in calculation: s = 82.06; BaCl2 =20g.2s

Table 4: Timing Table (weighing-To-Constant-weight of crucible plus

Precipitate)

HEATING COOLING
Time Stop Time Start
Needed Needed
50 min 15 min
30 min L5 min
30 min 15 min
30 min 15 min
30 min 15 min
30 min 15 min
 2A

-N;fu-r'>/:Zb?'D'%e4<2-2:[email protected]

b Abhined

.i

J
?

lVeight

M&ih 5: Summary of Results

ttu -*'eight of container

-*-eight of container
minus sample -;
',t-eight of sample --i
rveight of crucible plus ppt.* I

%i
weight of empty cmcible
',veight of ppt.

S
wt.ofBaSO,r x
B=*soaxloo**
%s= wt., of==
sample

= precipitate; *lMolar Weights: S = 32.06; BaSOa 233.40

=
 zl

ST.\T]ST|CAL EVA|_UAT|ON OF RTSULTS (% sl,

b{earu x
hfiedian, M
Shandard Deviatiory s
Rr{. Std. Deviation (RSD), %
ff. Deviation of the Mearu S

MIPORTED VALUE (% S)
 ?2

Actiaitv No. 4

DETERfuIINATION OF THE VOLUMETRIC

RATIO
DF HYDROCHLORIC ACID AND SODIUM
HYDROXIDE SOLUTIONS

The neutralization reaction between hydrochloric

acid and sod.ium
ir 'crodde solutions can be rnade to occur in a titration
process.
s ouanfitative, and is complete at the equivalence point whic]rThe reaction
is detected
rcugh a change of color of phenolphthalein indiqator.

The equation for the titration reaction is

HCI(aq) + NaOH(aq) NaCl(aq) + H2O, or simply

-->
H+ + OH- HzO
-->
ln this activity, the volurne of sod.ium hydroxid.e solution
needed to react
-"u:'ff a given
volume of hydrochloric acid solution is determined. From
this
r:cr:nnatioo the volumekic ratio of the acid and base
solutions is calculated.
'q:Er standardization of either solution, the normaiity of the other
can be
:a-culated Oo: this ratio.

TR,OCEDURE:

: Preparation of 0.1 Nonnal Solutions (0.1 N HCI

and 0.1 N NaOH)

4 --"1 N Hydrochloric Acid Solution (500 mL)

: ueasure out into a l-liter conical flask around 600

mL of distilled water.

: Heat the water to boiling, then cover the flask with

an inverted beakel,
and cool under the tap. Arternativery, coor by immersing
in an ice-water
bath on a basin.
I Transfer around 300 mL of the boiled water into a previously
cleaned 500-
nL volumetric flask (Figirre L0).
 23

*1 1:j. .i mL of concenkated HCt (12 N) into

the flask. Then add more of
: = boiled water until the 500-mL mark is reached.

::roper the flask, and mix the solution well by inversion

and shaking.

l::.a11y, transfer the sorution into a rabered and

stopperedbottle. To label,
-:"ircate (on the iabel) the concenkation and formula
of the solution,
r -rr name and class sectiory and the date
of preparatio4 as shown below.

0.1 N HCI
Juan A. dela Cruz
Chem 28.2-ABC
Jan.19,2004

--riter labeling, present your prepared solution to your instructor

/o r
.:r'troaal (if approved, he affixes his signafure in the corresponding
:f,ace in the answer sheet.)

- I lf Sodium Hydroxide Solution (500 mL)

i.epeat procedures (1), (2), and (3) above.

'sing a v'atch glass, weigh around 2.5 grams of solid NaoH onplatform
a
:aiance. (solid NaoH absorbs moisfure rapidry, so do
the weighing
procedure quickiy and close the NaoH
container immediately).

Jissolve the weighed NaoH with the boiled distilred

water in a small
ceaker.

Transfer the resulting solution into the vorumetuic frask.

Then add more
oi the boiled water trntil the 500-mL mark is reached.

Repeat procedures (A.s) to (A.z) above. Be sure to use a solid rubber

slopper for this solution.
U" Jreaning of Burets (Acid Buret and Base Buret)

f,uret (Figure 11) is considered clean if distilled water drains freely from
-'r'
ff." !Let, and does not leave droplets adhering to the inner side. Before
:-dnr:ig, check first the stopcock of your buret for proper lubricatiory and be
r;-i: *dt the bore and tip are clear. To clean your buret, apply a lukewarm z%
:=:ergent solution (dissolue 2 grams detergent in g8 mL tap u;ater in a
beaker
;-:': iieat until with a tong-handled buret brush. Rinse
lukewarm) and scrub
::--.r.' times with tap water until the detergent is washed out. Rinse again,
i*- s :rne with disflled water and observe if droplets of water
still adhere to
r ' ,:ner side. (If so, apply another round of cleaning with the detergent
-:--f,on and rinsing with tap water and then with distilled water until
r::-ets of water no longer adhere to the inner side of the buret). Finalty,
** r--"' the cieaned buret to dry by attaching to the buret clamp or holder upside

I" Reading a Buret

Before doing Part fV, your instructor

will first demonstrate to vou how
'r: ::ad a buret, using his illustrations
*'"i;i filled with distilled water. Note that the buret a real a*"t
on the board, or (demo
has ten scale divisions
milliliter points, and thus shouid be read up to 2 decimal places,
Iqr'"''€€rl each
I; j'63 mL or 23.78 mL (recall Figure 11). Practice making readings with the
''-:trvision of your instructor using the demo buret fiiled with distilled
' ::ir' Your instructor will change the water level in the buret for eaeh
;-*;:ent duri4g this exercise.

To avoid parallax errors while read.ing, make sure that your

eyes are in
f : sarne level as the lower meniscus of the solution in the buret. It is most
*+r::ui to cast a shadow on
the bottom of the meniscus by means of a colored
"r jarkened area on a card (buret reader) held just behind the
buret, with the
:-:rred or darkened area slightly below the meniscus (Figure 12). your
;-s:uctor will show you an example of a buret reader which you should
r:-':e yourself. Present your buret reader to your instructor for approval
:;iing the next meeting of your class. (If approved, he affixes his signafure in
r: corresponding Epace in the answer sheet.)
 25

* ;rumetric Ratio Determination

i;:.se your acid buret (previously cleaned with z% lukewarm d.etergent

.:-u[on) two times with 5 mL portions of your prepared 0.1 N HCI
-.:-';tion. Discard the washings.

I l': ie sarne for your base

buret (previously cleaned as above) using your
-=:ared 0.1 N NaOH solution.

:l 'ire acid buret with the HCl solution and the base buret with the
','3I{ solution. Displace any air bubbles from the tip of the burets.
l-,",stilt your instructor on how to remoae the air bubbtes!)

'=3'rust theinitial readings of both burets to zero or near zero. Record. the
:=acings in the appropriate space in your answer sheet. (Test for leakage
:''' repeating the reading after atieast 5 min. No noticeabie change in the
:=ading should have occurred if there is no reak. otherwise, fix the
.:a<age problem).

";:te:
:-: this point, usingthe first student set-up which is ready, yaur instructor
;t:culd conduct a one-time titration denrcnstration
for the entire class,
': -'owing the rest tf the proced,ure (starting ftrm procedure lv.s),
:iiowing the proper use of the right and. teft hands during titratian, the
:,cper way of grasping the stopcock of a buret (Figure 73), and how the
:,;d point ls reached).

Deliver from the acid buret around 20 mL of the HCI solution into a
previously cleaned 250-mL erlenmeyer flask. Rinse the inner sides of the
l-lask with small portions of previousiy boiled distilled water (contained
:n a small plastic wash bofHe) to wash down any actd into the main
solution.

Add three drops of phenolphthalein indicator into the solution.

 26

Titrate the HCl solution with the NaoH solution

in the base buret to the
e:pearance of a faint pink col0ration as the end point
. For better resurts,
:re titration shotuld be dane against a white background
such as a white
:;per.

ln case the end point is overrun, add more HCI

until the solution
3,ecomes colorless again, then continue the
titration with NaOH, this time
:lop by drop.

'liren the end point is reached, record the final readings in each buret.

fo three trials. carcutate and summarize the resurts in your answer

sleet. (l{ofe; For your canaenience, the second column
of the data table
j:oirs results of sample calculations.)

rilur:tg- g'1ces;

di,luiliir 5* A', Ir. and undentrood, A. L., Laboratory Manuar:

euantitatiue
#,. ?*.i .Jsis, Sixth Edition, prentice-Hall, New jersey (l.ggl),pp.
10_12.

':rrJfory L. F. and simpson, s. G., euantitatiue Chemicar Anarysis, lzth

Edition, The Macmillan Company, New york (1,g70),pp.
155_156.

i-ristian, Guty D., Analytical chemistry,

John wiley and sons, rnc., New
\ ork (1994), pp. 681-683.
 27

flgure 10. A volumetric flask.

r u :.::;al. volumetric flask is

shown in Figure i.0. The flask
iliir.';.:-i the stated volume whe^ filled so that the bottom
of
'3rrr :::.itrrls coincides with the etched line.
I i : .-T.E:ric flasks are never used for measuring
out solutions
l:riiJ : -_:,er containers; they are used whenever
it is desired to
r!,iL1rd ; rolution up to an accurataly known volume.
DIir'! *c- solutions are made up i* volumetric flasks, it is
:;J,::*-nnt that they be well mixed. This is accomplished
by
"rme;:edly inverting and shaking the
flask.
5:":: -.r:ons should
not be heated in volumetric flasks. There is

" ;,::'.:rsility that the flask may return to its exact original
rr'1,1.*L€
^ot
upon cooling.
. /,.-ir. a solid is dissolved in a volumetric
flask the final
Conloins
: '-:.e adjustment should not be made until all the solid has 500 mi
ns.":.';ed (Day and Underwood, pp. 2O"C
12_13).

I t_)
20'c
ml Figure 11. A buret.

oAcommon form of buret

is shown in Figure 11. The buret is
used to deliver accurately known but variable volumes,
mostly in titrations. The stopcock plug is made of
either glass
or Teflon. The teflon stopcock requires no lubricatiory
but the
glass plug should be lightly greased with stopcock
grease.
rTo lubricate a stopcock, remove
the plug and wipe old grease
away from both plug and barrelwith a cloth or tissue. Make
sure the small openings are not plugged with grease.
Then
spread a thin, uniform layer of grease over the
plug. Finally,
insert the plug in the barrel and rotate it rapidly in place,
applying a slight inward pressure. The lubricant should
appear uniform and transparen! and no particles of grease
should appear in rhe bore (Day and Underwood, pp.
10_11).
 28

Cord

Meniscus
Eye levet

Dorkened oreo

IlEure 12. Card for heip in reading a buret (buret resder).

The eye should be level with the bcrttom
of the meniscus. Here, the reading is
1.42 mL (Day and Underwood p.tZ)
,

Figure 13. Method of grasping stopcock.

In performing titrations, the student sirould develop
a techruque that permits
both speed and accuracy. The solution
being titrated, generaliy in an erlenmeyer
flask, should be ge^tly swirled as tire titrant
is derivered. one way to
accomplish this, i+'hile retai^ing control of
the stopcock and permitting ease of
reading the buret, is toface the burct, with
the stopcock an ilrc right, and operate
(grasp) the stopcock with the left hattd
trombehind the buret while swirling the
solution with the rigrtthard (Figure 13). T'he
thumb and forefinger are wrapped
around the ha.dle to turn tire stopcocrg and inward
pressure is appried to keep
the stopcock seated in the barrel. The last
two fingers push against the tip of the
buret to absorb the inward pressure. (Day and
Underwood, p. 10 and r.2).
 79

Actioity No. 4

DETER]VIINATION OF THE VOLUMETRIC RATIO

fF HYDROCHTORIC ACID AND SODIUM UYNNOXIDE SOLUTIONS
-
w:.itctor's Approaal signatures for the prepared solutions and
Buret Read.er:
; NaOH: ; Buret Reader:
: "{:.{ AND RESULTS:

fiitln,i*
:eading, mL HCI 25.24
mn;- reading, mL FICI 0.01
'r-olume, mL HCI 25.23
'*:t

er":- reading, mL NaOH 23.96

*m;:J reatling, mL NaOH 0.02
",,et -;olume, mL NaoH 23.94

:rL HCI * ? mL NaOH 0.9489

:rL NaOH ' ? mL HCI 1.054

- "TST]QAL EVALUATTON OF RISUL]S {RAT|OS):

f{6ear Values:
*-t-t. mL HCI = ? mL NaOH mL NaOH
."..t-r- mL NaOH - ? mL HCI
mL H0

hMctlian Values:

- ".t,LmL HCI - ? mL NaOH mL NaOH

: -n:0 mL NaOH - ? mL HCt mL HCI

REPORTED VALUES:
-j00mLHCI- ?mLNaOH mL NaOH
-.J00 mL NaOH - ? mL HCI mL HCI
 Activity No, S

STANDARDIZATION OF SODIUM HYDROXIDE ACAINST

POTASSIUM ACID PHTHALATE KHP)

-:' standardizatiory the concenkation of a certain acid or base soluti,on is

*::-:ately determined by usually reacting it with a known weight of
a
:*-:{' standard in a titration process. A primary standard is a solid
**r:inc€ of usually at least 99.9% purity which is used for
the direct
'n'-
j*dization of a given solution. For standardizing base solutions, a
-]*:.:er of acid primary standards are available such as
potassium acid
t*:-'lafg, benzoic acid, and potassium biiodate.

--:tassium acid phthalate (abbreviated as KHP) is the monopotassium salt

;r :.-':alic acid. Its chernical structure is drawn below. It is readily
available
:: :'jnty of 99-95% or better from chemical supply houses. It is stable on
;: "-:.9, nonhygroscopic, and has a high equivalent weight of.204.2J.

COOH

COOK
potassium acid phthlate (KF{p)

Lr this experiment, the concenfuation of sodium hydroxide solution is

:,::::-mined using KHP (chemical forrnula: KHscaoq; Moiar weight z04.zg)
'r- i,e primary standard. From the weight of the standard used and the
' -:ie of NaOH solution required during titration, the normality of the
r'- H solution can be calculated.

T'; ]{EDURE:

ln' the standard KHP on a watch glass in an oven at 110-i.20oC for at least
-:;e h.our. Place in an air-tight container and store in a desiccator when
- :: needed. Alternatively, the sample will be provided to you pre-dried
, :eady, contained in a weigting bottle, ready for procedwe
2.
 31

l" eigh accurately by the rnethod of difference

into each of tlree clean and
-:.leled (I, lt, ilI) 250-mL erlenmeyer flask 0.50xx g (where
x couid be any
:':nber) of the previously dried potassium acid phthalate.
Record the
i\ erghts in your data notebook.

To each flask add S0 mL of distilled water (preferably previously

boiled)
irom a graduated cylinder and swirl the flask gently until the sample
is
dissolved.

{- Add 3 drops of phenorphtharein indicator to each flask.

! Rinse and fiIl your burets with your previously prepared HCI and NaoH
solutions.

n Record the initial readings of both burets.

l:trate the solution in the first flask with the NaOH solution to the first
ippearance of a permanent pink color as the end point.

-:' case the end

point is overrun, back-titrate with the HCI solution in the
acid buret. In such case, don't forget to take the final
reading of the HCl,
and convert the net volume of HCI to volume in terms of
NaoH from
--:e volumetric ratio
of the two solutions. Then subtract this volume of
jiaoH from the voiume of NaoH delivered
to get the net volume of
liaOH.

r R.ecord the final reading of the NaOH solution.

"; R.epeat the tihation using the remaining two sampres.

4 ttt r ence:

rr.nrr-"ion,L. F. and simpsory s. G., euantitatiae Chemicnl Analysis, 12th

:::tiory The Macmillan Company, New york (IgT0), pp.16J_1,66.
rur''' R..A. Jr. and underivood, A.L., Laboratory Manual:
euantitatiae
;-,'.stysis,6th Edntrorv New )ersey (1991.), pp. 44_45.
 5,r.

Actiaity No. 5

STANDARDIZATION OF SODIUM HYDROXIDE ACAINST

POTASSIUM ACID PHTHALATE (KHP}

AND RESULTS: .

m
bottie with standard
bottle with std minus std
of standard taken

ilii:,i :eading, mL NaOH

lrni: i :eading, rnl NaOH
, ,, -T.€7 mL NaOH

Null : ,: -l itratian:
il,::-,,a* reading, mL HCI
li:: i ieading, rnl HCl
i,*-'l€, mL HCI

il*I:",--'Fram Preaious Actitrity):

1,:-_HClr mL NaOH ,,;'

,llrr
-r€ of HCI in terms of NaOH, mL

-;olume Of NaOH, mL
'u.:

k" : *lated Concentrations:

-:=ralify of NaOH
r4;.;-rif of NaOH

''r:r:ralitf of HCI
i:-.r"'of HCi
 33

T \TI STI CAL EVALUATION

:
OF RES U LTS (N]O R]VIAL ITY} :

llh(ean Values:
,'::a:1 Normalily NaOH N
';=":r )Jormality HCI N

lludedan Values:

rrro:rAan Normality NaOH N

lLrl*:i an Normaiity HCI
N

il]iFORTED VALUES:
",u:fll'dJit/ NaOH N
-:::.a1ity HCI N
 Actiuity No. 6

DETERIVIINATION oF TT{E TOTAL ALKALINE STRENCTH

OF AN IMPURT ALKALI CARBONATE

The determination of the total alkaline sken gt}- of. soda ash (impure
sodium carbonate, Na2co3) or of pearr ash (impure potassium carbonate,
KzC:) is a typical alkalimebic process. Here, the sample is tihated with
standard hydrochloric acid to the methy red or methyl orange end
point. This
gves a measure of the total alkalinily of the sample, which is
mainly due to
*.e carbonate constituent. Although there may be small amounts
of
nYdroxide and bicarbonate constifuents which also contribute to
the total
slkalinity, results are usually expressed only in terms of percent Na2O (Molar
rteight = 6'l'-98 g/mol) or percent Kzo (Molar weight 94.20 g/mol)
= depending
::. the samplp.

The chemical equation for the titration process is (in the case of sod.a ash):
Na2CO3(aq) + 2HCl(aq) 2NaCt(aq) + H2O + Cek)
-f'
?R.OCEDURE:

:' Dry the given unknown sample on a watch glass in an oven at 110-120oC
for at least one hour. Place in an air-tight container and store in a
desiccator when not needed. Alternatively, the sample will be provided
to you pre-dried already, contained in a weighing bottle, ready for
Procedure 2.

Accurately weigh by difference triplicate samples (I, il, III) of about 0.20xx g
each (where x could be any number) of the previously dried unknown
sample into three labeled 2S0-mL erlenmeyer flask.

Dissolve each sample in abor.lt 50 mL of distilled water, and add 3 drops of

methyl red indicator. (Methyl red is red in acid and yellow in basic
solution.)
 \
Titrate the first sample (Sample I) with your previously
standardized HCI
solution. Don't forget to record the initial buret reading of
HCI before
hitration.

As soon as the solution is distinctly red, add 1 mL

more of the HCl fron
the buret, and boil gently for about 5 minutes to
expel the carbon dioxide
from the solution.

6. Cool the soiufon to room temperafure, and

continue fhe titration to the
equivalence point, using either the standard
HCI (procedure za) or
standard NaoH (procedure Tb), depending on
the colar of the solution
after boiling.

7a. If insufficient acid is present to compretery convert

bicarbonate into
carbon dioxide and water, the indicator will furn
back to its basic color
(yellow) as the carbon dioxide is expelled. The
tilration is then continued
with the standard HCI solution.

7b. If excess HCI is presenf the indicator will retain the acid color (red)
and
the solution is back-titrated with the standard NaoH
sorution. (Don,t
forget to record the initiar buret reading for NaoH
before titration.)

In either case above (za wtd.Tb), the endpoint shourd

be the appearance of
a color between red and yeliow.

'. Record the final buret readings for HCI and NaoH solutions.

- 1. Repeat the tikatio', using sample II and then sarnple III.

^1' From the volumes of acid and base emproyed in the tikatioo and
the
data derived from ratio and standardization determinations,
calculate the
alkaiine sfrength of the sample in terms of % NazO or
% KzO.
?.eference:
-iamiltoru L- F. and simpson, s. G., euantitatioe chemical Analysis, 1,2fh
Edition, The Macmillan Compffiy, New york (i.gll), pp.l7Z-175.
 35

Actiaity No. 6

DETER]VIINATION OF THE TOTAL ALKALINE

STRENCTH
OF AN IMPURE ALKALI CARBONATE

Errar, /o
Rattng, %

Deductions, %

Net Rating, %=
DATA AI{D RESULTS:

Example

Ift. of bottle + sample, g 35.5124

'rr't. of bottle +
sample minus samplg g 35.3106
lYeight of sample taken 0.2018

Final reading mL HCI 36.85

Irdtial reading, mL HCI r.32
Volume, mL HCI 35.53

tsack-Titration:
Final reading, mL NaOH 1,.92
Iniliat reading, mL NaOH 0.84
\-olume, mL NaOH 1.08

Ratia Fram Preaious Activity:

..000 mL NaOH
= mL. HCI 1.084 '.

\-olume of NaOH in terms of HCl, mL 1.1,4

-\et volume of HCl, mL u.39

 37

F,om Preuious Actiaity:

Srrmaiily of HCI = 4J206

Jalculated. P er cerctage:

63.6e %

or /o K2O, depending on the sample given. Ask your instructor for

the type of sampie.

STATISTICAL EVALUATION OF RISULI-S (f" Na2o):

Mean, i
Mediary M
Standard Deviatiory s
Rel. Std. Deviation, RSD (%)
Std. Deviation of the Mean, S

REPORTED VALUE (% NazO)

 38

Actiaity No, 7

DETERTVilNATTON oF AcETrc AC|D

CONTENT
OF COMMERCIAL VINECAR

The principal acid in vinegar is acetic acid and most commercial vinegar
'r":cards require at least 4% aceh,c acicl content. The total quantity
of acid can
:* :eadily deterrnined by titration with standard
base using phenolphthalein
:-:-cator' Although other acids may be presen! the
result is calfllrated
r-::iv as acetic acid, HCzHge (Molar weight: 60.05
g/mol).

Ihe chemical equation for the titration process

is simply
i{C2H3Q(aq) + NaOH(aq) ---* NaCzHgO2(aq)
+ H2O

rI ]CEDURE:

Clean and dry three 2b0-ml erlenmever flasks. Mark as I, II, and III
:espectively.

each flask accuratery. Record the weights in the corresponding

"\'eigh
;race in your data notebook.

-sing a clean transfer pipetor measuring pipet (Figure 14 and Figure 15),
:eiiver 5 rnl. of vinegar sample into each flask"

each flask containing the sample accuratery.

"'-eigh Record the weights
-:. vour data notebook.

.dd 2 drops of phenophthalein indicator into each flask.

l:irate the first sample (Flask I) r+'ith standard NaoH

solution to the first
:ennanent faint pink color (the end point). Remember
to record. the
-ritial buret reading before tikation. (Note: Titrate sloutly and carefully
:')ten approaching the end point, in arder to auoid back-titration which
::mplicates yaur calculatians! ! !)
 39

when the end point is reached, record the finar reading.

If the end point is overrun (sorution is intensely pink in color), you

have
tre option to back-titrate the solution with your
standard HCl.
iemember to take the initiar buret reading before beginning the
back-
titration. lvhen the solution furns colorless, stop the back-tikation, and
conflnue the tikation with the standard NaoH until the end point is
reached. In this case, record the finar readings of both NaoH and HCI
solutions.

Repeat procedures (6), (7), and (7a) above, using the remaining
two
samples"

From the volumes of acid and base emproyed in the titration, and the
Cata derived from ratio and standardization determinations, calculate
the
rercentage of acetic acid in the vinegar sample.

: t."erence:

J ar-, R. A. Ir. and underwood, A. L, Laboratory Manunl: euantitatiae

Analysis,6th Edition, Prentice-Hall, Inc., Ner,v Jersey (j.ggl), p. 52,
 t 40

Figure 1.4. Types of Pipets: (a) transfer pipet, (b) measuring

o TD l0m
20"c
pipet. (.) n
ll
.Iyo c\J t\
:o*Ton types of pipets are shown in Figure 14. c rl
{l
' L-ne.transJer ptpet is used to transfer accurately known volume of tlt*:-i
solution from one container to another. ;F
tMeasuring pipets are graduated much
like burets and are used for |€
l:rl

measuring volumes of sorutions more accurateiy than O-

could be done
with g.raduated .cylinders. However, *eus,.rrir.,g pipets are not
l:d
l:l
ordinarily used where high accuracy is required. t=-l
L:J
rThe pipet should be cleaned if "distilled
water does not drain t-i-l
l:l
uniformly, but leaves droplets of rvater adhering to the t-=t
inner surface. tl
9_l"9rung can be done with a warm solurion oT d.t".gunt lbny u.,a
Underwood,pp.T-B)
\lU
(b)

Figure 15. Filling a pipet: (a) liquid

drawn above graduation mark,
and, (b) use of forefingers to
adjust liquid level in pipet.

The pipet is filled by gentle suction to about 2

cm above the etch line [Figure 15(a)]. The tip
of the pipet should be iiept *"U't"to--tir.
surface of the liquid during the filling
operation. The forefinger is then quickl!
tl*:.d over the top of the pipet [iigure
i5(b)1, and the solution is allowed-to druin out
until the bottom of the meniscus coincides
with the etched line. Any hanging droplets
of solution are removed by-touchi"ng"thetip of
the pipet to the side of the beaklr, and.'the
stem is wiped with a piece of tissue paper to
remove drops of solution from the -outer
surface. The contents of the pipet are then
allowed to run into the aesirea container,
yjll ::* being. taken to avoid spaftering.
rvrtn the plpet in a aertical position, allow
the solution to drain down the inner wall for
about 30 sec after emptying, and then fouch
the tip of the pipet to the inner side of the
receiving vessel at the liquid surface. A
small volume of solution wltt remain in the
tip of the pipet, but the pipet has been
-
calibrated to take this into acioun0 thus this
small final quantify is not to be blown out ar
otherwise disturbed. pipets with damaged
tips are not to be trusted (Day and
Underwood, pp.B-9).
 4L

Actiaity No. 7

DFTERN4INATION OF ACETIC ACID CONTENT

OF COMMERCIAL VINECAR

Er-ror, /o

Rattng, %

Deductions, /o

Net Rating, % =

- AIA AND RESULTS:

"".':. of flask (empty) g 122.1562

'i.
of flask plus sample, g 126.9658
',.:. of sample, g
4.8A96

--:"al reading, mL NaOH 34.94

.--:al reading, mL NIaOH 4.69
, : lume, mL NaOH
u.25

| ,;:',;-Titration:
"'':"al reading, mL HCI 1.52
:::al reading, mL HCI 0.02
, l-ume, mL HC1 1.50

;i;o From Preaious Actiaity:

-r-'l mL HCI = mL NaOH 4.9489

:riime of HCI in terms of NaOH, mL 7.42

' =; volume of NaOH, mL 3?.83

 42

From Previous Actiaity:

\ormaiity of NaOH : 4.1271

Calculated. P ercentage:
%r{]cfi\a2

STAT|ST|CAL EVALUATTON OF RESUL TS {%HC2H3Q}:

Mean, *
Mediaru M
Standard Deviatioru s
Rel. Std. Deviation, RSD (%)
Std. Deviation of the Mean. S

REPORTED VALUE (% Hc2r4sly

 Actiaitv No. g

DETER]VIINATION oF TI-JE VOLUMETRJC RATIO oF POTASSIUM

PERfu1ANCANATE AND FERROUS SULFATE SOLUTIONS

The reaction. between potassium permanganate and ferrous suifate

solutions is a typical oxidation-reduction which can be
made to occur
:uantitatively in a tikation process. In such titration, when
carried out in the
:resence of acid, the permanganate ion (Mnoa-) is reduced
to manganous ion
\In++), which is colorless in dilute solution, while the ferrous
ion (Fe++) is
--'dized to ferric ion (Fs3+;. one drop of excess permanganate (which is
deep
:'"r-'ple in color) imparts a very definite pink color to
the solution. The
apPearance of such a color is taken as the end point.
The reaction involved is

MnOa- + SFe++ + 8H+ ---+ Mn++ + 5Fe3+ + 4H2O

in this experiment, the volumetric ratio of the two solutions, KMnOa

and
FeSOa, is determined. If one of the soiutions
is standard.ized against a
rimary standard, the normality of the other can be calculated from this ratio.

]R.OCEDURE:

T
L Preparation of Solutions (0.1 N KMnOa and 0.I N FeSOa)
l 0.1 N Potassium permanganate Solution (500 mL)

Weigh approximately 1.8 grams of solid KMnOa (using a platform

balance) and dissolve in distillecl water in a 500-mL
beaker or flask to
make 500 mL,of resulting soiution.

Heat the resulting solution to boiling and then keep the temperafure
to
just below the boiling point for one hour.

Ifthe volume of solution has decreased, add distilled water

until the
volume is back to 500 rnl. Cover and ret stand overnight.
 M

Filter the solution by suction using a filtering crucible (Figure

L6) such as
a fritted glass crucible or a Gooch crucibie provided
with an asbestos mat
(or an equivalent set-up recommended by your
instructor). Take care that
the soluHon does not come in contact r,vith rubber materials during
filtration.

store the solution in a clean and property-rabeled glass stoppered

bottre
and present to your insh'uctor for.approval. Always keep
permanganate
solutions in the dark when not in use. (Reason: Light
induces the
decomposition of Mnoa- resuiting in the d.eposition of
Mno2 according
to the reaction 4Mnoa- + 2H2o 4Mnoz(s) + 3oz + 4oH-)
-->
0,1 lV Ferrous Sulfate Solution (250 nL)

Weigh approximately 7 grams of FeSOa.THzO into a 25Q-mL

beaker
containing 8 mL of 6 N H2soa a.d dissolve (by stirring) in
enough
distilled water to make 250 mL of resulting solution.

: Store the solution in a clean anJ properly-labeled glass stoppered.

bottle,
and present to your instructor for approvai.

iI Volumetric Ratio Determination

Rinse your acid buret (previously cleaned in the proper *"y)

two times
with S-mL portions of your prepared 0.1 I{ KMnoa sorution.
Discard the
rvashings' (The permanganate cannot be used in burets
with rubber tips,
because a reduction takes place upon contact with
the rubber).

Do the sarne for the base buret (previously cleaned in the proper
*uy)
using your prepared 0.1 N FeSOa solution.

Fill the acid buret with the KMnOa solution and the base buret with
the
FeSOa solution.

Adjust the initial readings of both burets to zero or near zero. Record
the
readings.
 45

5' Deliver around 30 mL of the ferrous solution

into a ciean 250-mL flaslq
and add 10 mL of 6 N H2soa. Titrate
with the permanganate soiution
until a faint pink color is obtained which
persists even after swirling the
solution for 15 seconds.

6. when the end point is reached record the

finai reading in each buret.

7 ' Do three t'ials' Calculate a'.d. summarize

the results in your answer
sheet' (Nofe; For your conaenience, the
second colurtn of the data table
shows results of sanqtle calculations.)

References:
Day, R.A. and underwood, A. L.,
Laboratory lulanuar: euantitatiae Analysis,
Sixth Editioru prenctice-Hall, Inc., New
Jersey (1gg1), p.20.
Hamiiton, L' F' and simpson, s. G.,
Quantitatiue Chemicar Anarvsis, L2th
Edition, The Macmillan Company, New york (1,970),
pp. ZtS_itS,.'
,---*-_-\,
f__----2 r-___\ A
\ l\liYtt I
I l,----
,_--_____\

\\--=1
\@/ ^tt
I \,_LJ
,-'l
i

(o)
tb)
tr3 tr3 (c)
)

To ospiroror

(d) (e)
Figure 16. Filtering crucibles and set
up.
(a) Gooch; (b) porous porcerain; (c)
fritted gias.s, high and low forms; (d) walter
holder; and (e) set up for fiitration with suction
using Walter holder,
(Selected figures from Day
and Underwood, p. 20)
 qo

Actiaity No" 8

DETERTVIINATION OF THE VOLUMETRIC RATIO OF POTASSIUM

PERfuIANCANATE AND FERROUS SULFATE SOLUTIONS

I":t!y!t-?r's prepared Solutions:

_Approaal Signatures for the
,.i N KlvInO4: ;0.1 N FeSOa:
DATA AND RESULTS:

Example

lnal reading, mL KMnOa 23.53

-nitial reading, mL KMnOa 0.20
i,. et volume, mL KMnOa 23.33

irnal reading, mL FeSOa 30.s4

-nitial reading, mL FeSOa 0.20
l'iet volume, mL FeSOa 30.34

- i00 mL KMnO+ = ? mL FeSOq 1.301

- 000 mL FeSOa = ? mL KMnOa 0.v690

_T,{Tt STt CA L EVALU ATTON O F RESU Lt-S (RAT| OS} :

lfean Values:
-.000 mL KMnOa = ? mL FeSOa mL FeSOa
-.000 mL FeSOa = ? rnl KMnOa mL KMnOa

\fedian Values:
-.i100 mL KMnOa = ? mL FeSOa mL FeSOa
- i100 mL FeSOa = ? mL KMnOa mL KMnOa

R,IPORTED VALUES:
-.J00 mL KMnOa = ? mL FeSOa mL FeSOa
- 100 mL FeSOa = ? mL KMnO+ mL KMnOa
 Actiaity No. 9

STANDARDIZATION OF POTASSI UM PERJVIANGANATE

SOLUTION ACAINST SODIUM OXALATE

Potassium permanganate is a very powerful oxidizing agent capable of

: 'jdizing many cations and anions such as ferrous ion, stannous
ion, nitrite
:i,
and oxalate ion to name a few. usually, potassium permanganate
*:iutions are prePared from commercial potassium peffnanganate which is
: --: sufficiently Pure. Such solutions therefore need^ to
be standardized
,:arnst a primary standard, the most common of which are sodium oxalate,
":senious oxide, and iron wire.

In this
experiment, potassium permanganate is standardized against
i--cium oxalate, Na2c2oa (Molar weight : 134.00). The reaction involved is

2MnOa - + SHzCzO4 + 6H+ ---+ 10CO2 + 2Mn++ + gHzO

:R.OCEDURE:

Dry the standard Na2c2oa on a watch glass in an oven at i.10-120oC for at

least one hour. Place in an air-tight container and store in a desiccator
when not needed. Alternatively, the sample will be provided to you pre-
dried already, contained in a weighing bottle, ready for procedure 2.

Weigh accurately by the method of difference into each of three clean and
labeled (I, IL III) 400-ml beakers hiplicate portions ot about 0.20xx g (where
x could be any number) each of the previously dried sodium oxalate.
Record the weight in your notebook.

Add about 200 ml of water and 30 ml of 6 N l{2soa into each beaker, and
stir until the oxalate has dissolved.

i Rinse and fill your burets with the KMnoa and Fesoa solutions.

Adjust and record the initial readings of both burets.

 48

Tikate fairly rapidly the first solution (Beaker I or Trial

I) with a volurne
of permanganate approximately G0 times the number
of grams of sodium
oxalate in the beaker (e.g., rz ml for 0.2000 g Na2C2oa).
stir the solution
vigorously during this titration, and disregard the
fact that it becomes
deeply colored from an apparent excess of permanganate.

Allow the solution to stand for a minute or so until the permanganate

color has disappeared. Remove and wash down the stirring
rod *im u
few drops of distilled water. [Nofe: If the permanganate
coior of the
solution does not disappear, excess permanganate has
been added. Lr this
case, discard the sorution for Trial I, and proceed
to Trial II and III (repeat
Trial I iater), this tirn.e using 40 times instead of 60 times
as d.escribed in
Procedure 6].

Heat the solution and monitor the temperafure with a

thermometer
placed in the center part (horizontal-wise and vertical-wise)
of the
solution. when the temperafure is aiready beh,'een ssoc and 60oc
continue the titration in that temperature range, adding
the
permanganate titrant drop by drop as the end. point
becomes nearer,
while stirring the solution with a glass rod. (Nofe: Do
not use the
thermometer for stirring! Approach the end point with
extreme care in
order to avoid any back-tibation).

Take as the end point the faintest visible shade

of pink that remains even
after stirring for L5 seconds. In case the end point
is overrun, back-titrate
with the FeSOa solution.

_,], Record the final readings in both burets. Then repeat

the titration process
starting with Procedure 5 for each of the two remaining
solutions.

R.eference:

i{amiltorg L. F. and Simpson, S. G., Quantitatiae Chemical

Analysis, 12th
Edition, The Macmillan Companf, New York (1,97q, pp.21.6-217.
 49

Activita No. 9

STANDARDIZATION OF POTASSIUM PERfu1ANCANATE

SOLUTION ACAINST SODIUN4 OXALATE

DATA AND RESULTS:

-aaii-*-a:E--
Wt. of bottle with standard 49.4227
Wt. of bottle with std minus std 49.2208
Weight of standard taken 0.2019

Final reading, mL KMnOa 20.97

Initial reading, mL KMnO+ 0.00
Voiume, mL KMnOa 20.97

Back-Titration:
Final reading, mL FeSOa 4.92
lnitial reading, mL FeSOa 0.36
Volume, mL FeSOa 0"s5

Ratio (Frorn Preaious Actiaity):

1.000 mL FeSO4 mLKMnOa I

Volume of Fe SO4 in terms of KMnO4, mL 0.43

Net volume of KMnO4, rnl

Calculated Concentratians:
Normality of KMnOa 0.1467
lfoiarity of KMnOa 4.02934

Norn-lality of FeSOa 0.1128

\Iolarity of FeSOa 0.1128
 50

STATI STICAL EVALUATION OF R.FSU LTS

NORMALITY) :

Mean Values:
Mean Normality KMnOa N
Mean Normality FeSOa N

Median Values:
Median Normality KMnOa N
Median Normality FeSOa N

REPORTED VALUES:
Normality KMnOa N
Normality FeSOa N