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Acid Base Buffers

Acid Base Buffers

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Acid-Base Buffer
Acid-Base Buffer

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LAREDO COMMUNITY COLLEGE

Science Department
CHEM 1412 Acid-a!e "##er! 1
CHEMICAL REACTIONS: ACID-BASE BUFFERS
Short Overview
Acid! and $a!e! represent two of the most common classes of compounds. Many studies
have been done on these compounds, and their reactions are very important. Perhaps the
most important reaction is the one in which an acid and base are combined, resulting in the
formation of water (in aqueous solution) and a !a%t; this reaction is called ne"tra%i&ati'n.
A $"##er !'%"ti'n is a solution that contains both an acid and a salt containing the
conugate base anion in sufficient concentrations so as to maintain a relatively constant p!
when either acid or base is added. "n this e#periment you will prepare a buffer solution and
observe its behavior when mi#ed both with an acid and a base. $ou will also compare the
behavior with that of solutions containing only the acid.
Theory
"n his theory of ioni%ation in the &''()s, *vante Arrhenius defined acids are substances
which form !
+
and bases as substances which form ,!
-
in water. !e further defined a salt
as a substance other than an acid or base which forms ions in aqueous solution. *uch
substances are thus capable of producing an electric current and are called electrolytes.
.he amount of electricity produced is directly proportional to the concentration of ions in
solution.
/ith regard to electrolytes we have learned previously that strong acids and strong bases
ioni%e completely, and are therefore strong electrolytes because they produce a large
electric current. *oluble salts are the other type of strong electrolytes. /e also learned
that weak acids and weak bases ioni%e only partially in solution, producing smaller
quantities of current; these substances are called weak electrolytes. Materials which do not
produce an electric current are called nonelectrolytes. .o complete our understanding, we
concluded that strong electrolytes e#ist primarily as ions in solution, while wea0
electrolytes e#ist as both ions and molecules in solution. 1onelectrolytes must e#ist as
polar molecules only in solution.
/hile it is useful, the Arrhenius definition of acids and bases is limited to aqueous
solutions. .his may seem insignificant to a student in introductory chemistry or general
chemistry, but it imposes restrictions for understanding more advanced topics. As such,
we now introduce two additional definitions of acids and bases, which e#pand our
understanding.
CHEM 1412 Acid-a!e "##er! 2
Acid a!e
Arr(eni"! forms !
+
in water forms ,!
-
in water
r)n!ted-
L'*r+
donates !
+
(proton) to base accepts !
+
(proton) from acid
Le*i! accepts electron pair from base donates electron pair to acid
.he r)n!ted-L'*r+ concept of acids and bases was introduced by 2ohannes 3r4nsted
and .homas 5owry in &678, and led to an understanding of many proton transfer
reactions observed to occur in both non-aqueous and aqueous solutions. 9ilbert 1ewton
5ewis quic0ly recogni%ed that a substance which is a proton acceptor must also be one
which contains an unshared valence electron pair to accept the positive charge. !e
therefore proposed his own theory of acids and bases based upon electron transfer rather
than proton transfer. .he Le*i! acid-$a!e concept is the most general and allows us to
understand reactions which may not involve proton transfer. !owever, the 3r4nsted-
5owry concept provides the simplest description of acid-base buffer solutions, and it is
this one which we will utili%e in further discussion.
/e will use the formula HA for an acid and B: for a base in our discussion.
Accordingly, the reaction between an acid and base is described by [1].
HA B:  :A
-
BH

[1]
"n the reaction above, the products which are produced are :A
-
. and BH

. :A
-
is called
the c'n,"-ate $a!e of HA because it has donated a proton (!
+
) to the base B: .5i0ewise,
BH

is the c'n,"-ate acid of B: since it has accepted the proton from HA. .he
substances HA and :A
-
are called a c'n,"-ate acid-$a!e pair. 5i0ewise, BH

and B:
are also a conugate acid-base pair. *ome common acid-base pairs are:
H
3
O
1+
/ H
2
O H
2
O / OH
1-
Hl / l
1-
H!O
3
/ !O
3
1-
H
2
"O
#
/ H"O
#
1-
H"O
#
1-
/ "O
#
2-
H
3
OOH / H
3
OO
1-
$acetate% !H
#
1+
/ !H
3
$a&&oniu&%
H
2
O
3
/ HO
3
1-
$bicarbonate% H
2
'O
#
1-
/ H'O
#
2-
$phosphate%
.he first two pairs show that hydronium ion and hydro#ide ion are the conugate acid and
base, respectively, of water. "t is the relative concentration of these two ions that
CHEM 1412 Acid-a!e "##er! .
determine whether a solution is acidic (;!
8
,
+
< = ;,!
-
<), basic (;!
8
,
+
< > ;,!
-
<), or
neutral (;!
8
,
+
< ? ;,!
-
<). .o accomplish this, we measure the pH of the solution. A p! >
@ is acidic, p! =@ is al0aline (or basic), and p! ? @ is neutral. p! is defined by the
equation
!H " -#o$
1%
[H
&
O

]'
An buffer solution must contain both a *ea/ acid and a salt of its c'n,"-ate $a!e. *ince
!Al, !1,
8
, and !
7
*,
B
are all strong acids, these substances will ioni%e completely and
their concentrations will be too insignificant to maintain constant p! values. ,n the other
hand, a wea0 acid such as acetic acid, A!
8
A,,!, only ioni%es to a small e#tent, so the
both the undissociated acid and its anion can e#ist in sufficient concentration in solution to
maintain constant p!.
/hen the acetic acid-sodium acetate buffer is prepared the following equilibrium is
established.
CH
&
COOH
0a12
H
(
O
0%2
 H
&
O
1
CH
&
COO
1-
[(]
.he equilibrium constant e#pression for the reaction is
3a 4
< A,,! A! ;
< , ! <; A,, A! ;
q) ( 8
&
8
- &
8
a
+
? &.@C # &(
-C
.
.herefore,
pH 4 p3
a
5 %'-
16








< A,,! A! ;
< A,, A! ;
q) ( 8
- &
8
a
7 [&]
Dquation [&] above is called the Hender!'n-Ha!!e%$ac( equation. .he equation shows
that because the acetateEacetic acid ratio does not change significantly during most
reactions, thus resulting in a relatively constant p!. /hen a strong base such as sodium
hydro#ide is added, the acetic acid in the buffer reacts with the hydro#ide ion to produce
additional acetate ion ([)]). /hen a strong acid such as !Al is added to the buffer, the
acetate ion will react with the hydronium ion to produce additional acetic acid ([*]).
CH
&
COOH
0a12
OH
1-
+ CH
&
COO
1-
H
(
O
0%2
[)]
CH
&
COO
1-
H
&
O
1

+ CH
&
COOH
0a12
H
(
O
0%2
[*]
.he predominant effect of the reactions is that the concentration of !
8
,
+
and ,!
-
do not
increase or decrease significantly during the reactions. !owever, continued addition of
1a,! will eventually consume all of the acetic acid present in the buffer, resulting in a
sharp rise in p!. 5i0ewise, addition of a large quantity of !Al will consume all of the
acetate ion in the buffer, causing the p! to drop sharply. .he amount of strong acid or
CHEM 1412 Acid-a!e "##er! 4
strong base that can be added to a given volume of a buffer system without a significant
change in p! (± & unit) is 0nown as the $"##erin- capacit+.
A buffer system such as A!
8
A,,! E A!
8
A,,
&-
is representative of an acidic buffer,
because the molecular component is a wea0 acid. ,n the other hand, a basic buffer
solution would contain the acid salt of a wea0 base in addition to the wea0 base itself. .he
1!
B
&+
E 1!
8
buffer is an e#ample of a basic buffer. 3iological systems use buffers to
maintain ambient physiological conditions. "n this regard the bicarbonate and phosphate
buffers listed earlier are the two most significant buffers of body fluids. (*ee the article
FAhemistry and 5ife: 3lood as a 3uffered *olutionG on page HH6 of he&istry( )he
entral "cience* +
th
,d.* 3rown, 5eMay, I 3ursten.
Jor more bac0ground information, you should review chapter &H FAcid-3ase DquilibriaG
in he&istry( )he entral "cience* +
th
,d.* .
E8erci!e 17 E8aminati'n '# t(e "##er 9r'pertie! '# a Dipr'tic Acid Sa%t:
9'ta!!i"m H+dr'-en 9(t(a%ate
K
+
O
OH
O
O
O
O
O
O
p'ta!!i"m (+dr'-en p(t(a%ate p(t(a%ate
A' Che,i-.#/ .01 A!!.r.t2/
he&icals: /ater
*olids: potassium hydrogen phthalate (K!A
'
!
B
,
B
, K!P, 7(B.77 gEmole)
*olutions: (.&( M !Al
$a-%
, (.&( M 1a,!
$a-%
(from Acid-3ase .itrations
e#periment), p! @ buffer solutions
.pparatus: 3alances, bea0ers, burets, buret clamps, Drlenmeyer flas0s, graduated
cylinders, hot plate, p! meters, ring stands, volumetric pipets, pipet
pumps, volumetric flas0s
"afety ,-uip&ent: goggles, gloves, hood.
Ob/ectives( "n this e#periment you will learn to:
CHEM 1412 Acid-a!e "##er! ;
&. prepare a (.&( M K!P solution from a solid and water
7. prepare a solution of the phthalate anion from (.&( M K!P and 1a,!
solutions
8. prepare a buffer solution containing both the hydrogen phthalate and the
phthalate ions
B. measure the p! of the buffer solution
C. measure the p! as !Al is added to the buffer solution
H. measure the p! as 1a,! is added to the buffer solution
@. compare the buffer solution with both a strong acid and a wea0 acid
B' 3ro-e12re
9art I7 9reparati'n '# S'%"ti'n!
CAUTION: Lse e#treme caution while handling the burets, volumetric pipets, and
volumetric flas0s.
0St"dent 12
&. ,btain 7C( m5 of distilled water in a B((-m5 bea0er from the M/ tap at the sin0
between the two hoods on the side wall. Add 8 teflon boiling chips to the water,
and boil the water for five minutes on a hot plate set on medium high. .his will
drive off dissolved A,
7
from the water which may interfere with the e#periment.
Allow the water to cool to room temperature.
7. ,btain a p! meter from the instructor. Nemove the rubber tip from the electrode
and place the electrode in a bea0er containing &( m5 of p! @ buffer. *oa0 the
electrode in the buffer solution for five minutes to condition the electrode. Miscard
the buffer in the sin0.
8. Nefer to the instructions for using the p! meter. *tandardi%e the meter to p! @.((
using a fresh sample of p! @ buffer.
0St"dent 22
B. ,btain the following items from the instructor:
& &((-m5 volumetric flas0, with stopper
7 burets, 7 buret clamps, and 7 ring stands
7 &(-m5 volumetric pipets, and pipet pumps
Attach the buret clamp to the ring stand.
C. Alean the flas0 with soap and water, and rinse carefully with two &(-m5 portions
of distilled water.
H. Alean the burets with tap water, followed by two rinses with distilled water. .hen
place each buret in the buret clamp on the ring stand. 5abel one of the burets
<NaOH= and the other one <HC%=7
CHEM 1412 Acid-a!e "##er! >
@. Alean the pipets with tap water, followed by two rinses with distilled water. 5abel
one pipet<A= and the other <=7
'. Pour &7C m5 of (.&( M 1a,! from the hood into a 7C(-m5 bea0er. 5abel the
bea0er. Necord the concentration on line &H of your lab report.
6. Pour '( m5 of (.&( M !Al from the hood into a &C(-m5 bea0er. 5abel the
bea0er.
&(. "f it is open, close the stopcoc0 on the <NaOH= buret. Lse a funnel to pour
appro#imately &( m5 of (.&( M 1a,! into the buret. Nemove the buret from the
buret clamp and roll the buret in your hands to allow the 1a,! to coat the inside
of the buret. Miscard the rinse into a 8(-m5 bea0er through the stopcoc0.
&&. Neturn the buret to the buret clamp and close the stopcoc0. 1ow fill the buret with
(.&( M 1a,! to one inch above the (-m5 mar0. ,pen the stopcoc0 to drain the
buret to (.( m5 in the 8(-m5 bea0er, thus removing any air bubbles in the buret
tip. Miscard the rinse into the sin0.
&7. Nepeat steps &( and && for the 4HC%G buret, using (.&( M !Al instead of 1a,!.
.he same 8(-m5 bea0er can be used to collect the drain.
0St"dent 12
'reparation of (.&( M 0H'
$a-%
.
&8. Lsing the electronic balance, obtain a sample of potassium hydrogen phthalate
(K!A
'
!
B
,
B
, FK!PG) with a mass between 7.( g and 7.& g. Necord the mass of
the sample to three decimal places in your noteboo0.
&B. .ransfer the K!P sample to the &((-m5 volumetric flas0, and dissolve in
appro#imately B( m5 of boiled distilled water. .hen add boiled distilled water to
the flas0 until the bottom of the meniscus is even with the mar0 on the nec0 of the
flas0. (Lse an eyedropper from your des0 to add the last few drops of water.)
&C. *topper the flas0, and turn it upside down three or four times to mi# the solution
totally. .ransfer the K!P solution to a clean 7C(-m5 bea0er. 5abel the solution as
you have been instructed.
&H. Metermine the concentration of the K!P solution.
'reparation of 1.122 M 0H' / 1.122 M 'hthalate ion 3uffer "olution.
0St"dent 12
&@. Lse pipet <A= to transfer 7C.( m5 of the (.&( M K!P solution prepared above
into a clean 7C(-m5 bea0er. Necord the volume on the lab report.
&'. Lse a graduated cylinder to add 7C.( m5 of boiled distilled water to the K!P. Mi#
the solution thoroughly.
0St"dent 22
&6. Lse pipet <A= to transfer 7C.( m5 of your (.&( M K!P solution into a clean &((-
m5 bea0er. Necord the volume on the lab report.
CHEM 1412 Acid-a!e "##er! ?
7(. Nead the volume of liquid in the buret to ±(.(C m5. $ou will need to estimate the
last digit; remember, buret readings increase from top to bottom. Necord the initial
buret reading on the lab report.
Ma0e certain your eye level is even with the bottom of the meniscus. A piece of
white paper behind the buret will assist you in reading the volume.
7&. Place the bea0er under the tip of the buret and add 7C.( m5 of (.&( M 1a,! from
the buret to the solution. *tir the solution as the 1a,! is added to thoroughly mi#
the solution. Necord the final buret reading to ±(.(C m5 on the lab report. .his
solution which you ust prepared contains (.(C( M phthalate ion.
77. Nefill the buret to the (-m5 mar0 with (.&( M 1a,!.
78. Pour the phthalate ion solution which you prepared into the 7C(-m5 bea0er
containing the K!P solution (*tep &', *tudent &). 5abel the solution as <"##erG.
$ou have now prepared &(( m5 of a buffer solution containing (.(7C M potassium hydrogen
phthalate (K!P) and (.(7C M potassium sodium phthalate (Fphthalate ionG).
9art II7 Mea!"rement '# pH and Determinati'n '# "##er Capacit+7
0St"dent 12
&. .ransfer &(.( m5 of (.&( M !Al from the buret to a clean &C(-m5 bea0er. Add
&(.( m5 of boiled distilled water to the bea0er. *tir the mi#ture and measure the
p! with the p! meter. Necord the measurement on the lab report.
7. Place the bea0er under the buret containing the (.&( M 1a,!. Necord the initial
volume of 1a,! in the buret to ±(.(C m5. Add &.( m5 of 1a,! to the !Al
solution. *tir the mi#ture and record the new volume of 1a,! in the buret and p!
on the lab report.
8. Add another &.( m5 of 1a,! to the bea0er. *tir and record the volume and p!
on the lab report. Nepeat this process until a total of &C m5 of 1a,! has been
added.
B. Miscard the solution in the sin0. .horoughly clean the bea0er with soap and water.
Ninse the bea0er twice with C-m5 portions of distilled water before proceeding to
the ne#t step.
0St"dent 22
C. Nepeat steps & O B above using pipet <A= to transfer &(.( m5 of (.&( M K!P
solution to the bea0er instead of &(.( m5 of !Al.
0St"dent 12
CHEM 1412 Acid-a!e "##er! @
H. Lse pipet <= to transfer 7(.( m5 of F"##erG to a clean &C(-m5 bea0er. *tir the
solution and measure the p! with the p! meter. Necord the measurement on the
lab report.
@. Place the bea0er under the buret containing the (.&( M 1a,!. Necord the initial
volume of 1a,! in the buret to ±(.(C m5. Add &.( m5 of 1a,! to the buffer
solution. *tir the mi#ture and record the new volume of 1a,! in the buret and p!
on the lab report.
'. Add another &.( m5 of 1a,! to the bea0er. *tir and record the volume and p!
on the lab report. Nepeat this process until a total of &( m5 of 1a,! has been
added.
6. Miscard the solution in the sin0. .horoughly clean the bea0er with soap and water.
Ninse the bea0er twice with C-m5 portions of distilled water before proceeding to
the ne#t step.
0St"dent 22
&(. Nepeat steps H O 6 above using pipet <= to transfer 7(.( m5 of <"##er= to the
bea0er. .itrate the buffer with (.&( M !Al instead of 1a,!.
C' Di/!o/.#
All solutions may be discarded in the sin0 with plenty of running water.
D' D.t. A0.#y/i/
Lse the graphing feature of Microsoft D#cel or Pernier 9raphical Analysis to create
graphs of p! vs. mmol added for each of the four titrations.

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