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Module 6 Chemistry Notes
Module 6 Chemistry Notes
Acid-Base Reactions
Topic Outline
3. Quantitative
1. Properties of Analysis
Acids & Bases
The titration technique
Acids, bases & indicators
Equipment, solutions, indicators
Acid reactions & applications
Titration calculations
Enthalpy of neutralisation
pH & conductivity graphs of titrations
History of Acid-Base Theory
Dissociation constants & pKa
Buffers... properties & importance
2. Using Bronsted-
Lowry Theory
Proton transfer & hydronium ions Strong & weak acids The pH Scale. Calculations
pH of strong & weak acids Self-ionisation of water Ion product & pOH Scale.
Amphiprotic water Acidic & basic salts Acid-base reactions without H3O+, OH- or H2O
pH change in dilution
3. Quantitative Analysis
The technique of titration. Aliquots & titres. Titration calculations.
pH & conductivity graphs during titration. Dissociation constants & pKa.
Buffers... properties, composition & importance.
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Acids and bases are chemical opposites; if you add A good example is the
one to the other they “destroy” (neutralise) each common garden plant
other, and the end product is neutral. Acids and Hydrangea.
bases are the opposite ends of a chemical property
called “acidity”, which is measured by a numerical If you collect a flower
scale called “pH”. head and put it through
a blender with a little
ACID NEUTRAL BASE water and ethanol, the
filtered liquid extract will
work as a simple
1 3 5 7 9 11 13 indicator.
pH
The word “acid” comes from the Latin for “sour”, In acid, the Hydrangea flower extract
and refers to the fact that natural, acidic chemicals is a bluish colour.
(e.g. vinegar) are sour-tasting. In a base, it turns pink-ish.
Indicators
Indicators are chemicals which change colour according to the acidity of the solution they are in. The
original indicators were natural extracts from plants or other living things. Some, such as litmus, are still in
use today, as well as newer, synthetically made chemicals.
®
Acids & Bases... Properties & Naming
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Laboratory Acids & “Alkalis”
You are reminded that the common laboratory acids are:
Typical Properties of Acids
Name Formula Chemical Name Solution of • mostly water soluble
Hydrochloric acid HCl(aq) Hydrogen chloride H+(aq)+ Cl-(aq) • sour taste
• corrosive & chemically reactive
Sulfuric acid H2SO4(aq) Hydrogen sulfate 2H+(aq)+ SO42-(aq) • react with bases to neutralise them
The most familiar laboratory bases are soluble hydroxide compounds which are sometimes called “alkalis”.
Typical Properties of Bases
Name Formula Chemical Name Solution of • bitter taste & “slippery” feel
Sodium hydroxide NaOH(aq) Sodium hydroxide Na+(aq)+ OH-(aq) • corrosive & chemically reactive
• react with acids to neutralise
Potassium hydroxide KOH(aq) Potassium hydroxide K+(aq)+ OH-(aq) them
The spectator ions remain in solution. If the solution sulfuric + copper(II) water + copper(II)
is evaporated, a solid ionic compound crystalises. acid oxide sulfate
(potassium sulfate in the example above)
Compounds like this are known collectively as H2SO4(aq+ CuO(s) H2O(l) + CuSO4(aq)
“salts”.
Continued...
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Acid-Base Reactions (cont.)
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Acidic Oxides of the Non-Metals Examples:
carbon dioxide + water carbonic acid
Many of the oxide compounds of the non-metal
elements are acidic because they will: CO2(g) + H2O(l) H2CO3(aq)
The different activity levels of the metals is clearly seen when metals are reacted with dilute
acids. You may do experimental work to observe how vigorously different metals
react with a dilute acid.
Metals like calcium and magnesium react vigorously. Zinc and iron are slower.
Lead is very slow indeed. Copper does not react at all. Bubbles of
gas are
When there is a reaction, the gas produced is hydrogen. (Confirm with a “pop test”) produced.
The metal is “eaten away” and dissolves into the liquid. This is because it forms a soluble A flame test
ionic compound. Exactly what the compound is, depends on which acid is used. gives a
“pop”
Examples explosion
zinc + hydrochloric acid hydrogen + zinc chloride The soluble ionic
Zn + 2HCl H2 + ZnCl2 compounds formed are
collectively known as
magnesium + nitric acid hydrogen + magnesium nitrate “salts”, so the general
Mg + 2HNO3 H2 + Mg(NO3)2
pattern of the
iron + sulfuric acid hydrogen + iron(II) sulfate
reactions is
Fe + H2SO4 H2 + FeSO4
Metal + Acid Hydrogen + a Salt
For all reactions encountered, you need to be able to
write full ionic equations, including states.
Acid-Carbonate Reaction
Acids react with any compounds containing the polyatomic ion carbonate, CO32-.
The products are always carbon dioxide gas, water and “a salt”.
Example
hydrochloric + calcium carbon + water + calcium
acid carbonate dioxide chloride
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Applications of the Neutralisation Reaction
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In Agriculture & Industry In Everyday Life
One of the most important industrial processes for Your stomach produces hydrochloric acid to help
our civilisation is the production of chemical digest the food you eat. Sometimes, it may produce
fertilisers. excessive amounts of acid which can cause
discomfort... “indigestion”.
Generally, these are made by the neutralisation of
the base ammonia (NH3) by an acid. The simple solution is to swallow a harmless
chemical which will act as a base and neutralise
One of the most important fertilisers is made by the excess acid.
reacting ammonia with sulfuric acid:
“Antacid” tablets often contain a non-toxic, non-
ammonia + sulfuric acid ammonium sulfate alkaline metal hydroxide, such as Al(OH)3.
You might not yet recognise that this is an acid- You should be able to figure this out as a
base neutralisation, but you will soon. neutralisation reaction.
Enthalpy of Neutralisation
The syllabus requires that you carry out an Reaction
experiment to measure the “enthalpy of The reaction has released heat energy,
neutralisation”. (exothermic) but to find the “Enthalpy of
Neutralisation” you must express this as
This is easily done with a simple laboratory the amount of energy released per mole of
calorimeter, a thermometer and solutions of reactants.
acid & base.
The reaction is:
Typical Method
1. Measure 50mL of 2.0 molL-1 HCl and HCl(aq) + KOH(aq) H2O(l) + KCl(aq)
(separately) 50mL of 2.0 molL-1 KOH
solution. The quantity of each reactant was 50mL of
2.0 molL-1 solution.
2. Measure the temperature of each solution.
If they are NOT the same, let them sit Since C = n/V then n = C.V
together until they equilibrate to the same = 2.0 x 0.05
temp. This is the starting temp. for the = 0.1 mol.
calorimetry calculation.
Enthalpy of Neutralisation
3. When ready, simply pour both solutions into the Therefore, the energy release per mole = 54,380 J
calorimeter. Stir, then record the final temperature.
ΔHneut = -54.4 kJmol-1
Typical Results
Starting temp. = 18oC
Further Discussion
The “accepted” enthalpy for this reaction is about
Final temp. = 31oC
-56 kJmol-1, so a result close to this is outstanding.
Is that the enthalpy just for that exact reaction?
ΔT = 13oC
Mass of liquid in calorimeter ≅ 0.1 kg Well, no.
(measure this for greater precision) If you write the equation in ionic form
H+ + Cl- + K+ + OH- H2O(l) + K+ + Cl-
Specific Heat Capacity = 4,183 Jkg-1K-1
(assumed the same as water) then eliminate the “spectators”:
H+ + OH- H2O(l)
Calculation it is obvious that the “essential” reaction is
between hydrogen & hydroxide ions. With minor
ΔT = 0.1 x 4,183 x 13
Q = m.c.Δ variations, this enthalpy will be the same for all
= 5,438 J of heat released. acid-base neutralisations.
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History of Acid-Base Theory
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The Bronsted-Lowry Theory
Early Ideas About Acids & Bases was developed independently by Johannes
Naturally occurring acids, like ethanoic acid in Bronsted (Danish) and Thomas Lowry (English) in
vinegar, have been known for thousands of years, 1923.
and described by their simple, observable properties
such as their sour taste. The basic concepts of this theory are not obvious.
You will need to read on into the next section, then
Chemistry became a modern Science just over 200 come back here as needed to understand it fully.
years ago, and one of the earliest scientific theories
about acids was put forward by
Acid-Base reactions involve transfer of
Antoine Lavoisier (French, 1780’s) Protons. ( = hydrogen ions, H+)
Lavoisier used simple plant-extract indicators Acids are Proton Donors.
(e.g. litmus) to identify acids and bases. He found by
experiment that all the non-metal oxide compounds
Bases are Proton Acceptors.
he tested produced acid solutions. He concluded
that acids must contain oxygen. Central to the Bronsted-Lowry (B-L) Theory is the
concept of “conjugate” species. For example, when
Humphry Davy (English, 1820’s) ethanoic acid dissolves in water:
Forty years later and armed with more chemical
knowledge, Davy realised that Lavoisier was wrong
CH3COOH(aq)+ H2O(l) H3O+(aq)+ CH3COO-(aq)
about acids. While some acids do NOT contain
oxygen (e.g. HCl), he found that all known acids
ethanoic + water hydronium + ethanoate
contain hydrogen.
acid ion ion
Davy also discovered that metal oxides are basic Acid Base Conjugate Conjugate
and described the patterns in the way acids react Acid Base
with metals to form hydrogen gas.
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δ+
C
δ+ δ−
Cl- δ− + δ− O
δ+
δ+ δ− This group is
usually
Separate, hydrated ions abbreviated
Cl-(aq) and H+(aq) as “-COOH”
and is always
acidic.
Although there may be many water molecules These C-H bonds are non-polar, and never ionise.
clinging to a H+ ion, for simplicity we imagine there
is just one, and it forms a special ion, called the
When this molecule is dissolved in water the
“hydronium ion”, H3O+.
O-H bond ionises, and donates a proton to a water
molecule:
HCl(g) + H2O(l) H3O+(aq) + Cl-(aq)
CH3COOH(aq)+ H2O(l) H3O+(aq)+ CH3COO-(aq)
HCl is an acid because it has “donated” a proton to
ethanoic + water hydronium + ethanoate
a water molecule. The hydronium ion in the solution
acid ion ion
is an acid because it can, in turn, donate a proton to
other species.
Notice that this reaction is reversible and typically
reaches a dynamic equilibrium which “lies to the
In water solution, left”, favouring the reactants.
all acids produce hydronium ions.
Now Complete Worksheet 3
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Strong & Weak Acids
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In everyday usage, a “strong” solution might mean In contrast, ethanoic acid is a WEAK acid; when
the same as “concentrated” (i.e. having a lot of added to water, the reaction...
solute) and “weak” can mean the same as “dilute”.
CH3COOH(aq)+ H2O(l) H3O+(aq)+ CH3COO-(aq)
FROM HERE ON, YOU MUST NOT USE THESE
TERMS THAT WAY. “Strong” & “weak” have ...reaches an equilibrium with only about 1% of the
particular meanings with regard to acids. molecules ionised. (i.e. the equilibrium lies well to
the left, favouring the reactant molecules.) If the
For example, HCl is a STRONG acid; when added to concentration of the solution was 1 molL-1, then the
water the reaction goes fully to completion. hydronium ion concentration would be only about
0.01 molL-1.
HCl(g) + H2O(l) H3O+(aq) + Cl-(aq)
It is quite possible to have a “concentrated solution
100% of the HCl molecules are ionised. of a weak acid” or a “dilute solution of a strong
If the concentration of HCl was (say) 1 molL-1, then acid”... just be careful with these precise meanings!
the concentration of hydronium ions will also be
1 molL-1. STRONG Acid = Total Ionisation in Solution
The pH Scale
You are already familiar with the pH scale in a
descriptive way. Example Calculations: pH and [H3O+]
ACID NEUTRAL BASE 1. If the concentration of hydronium ions is
[H3O+] = 0.500molL-1, what is the pH?
Solution: pH = -log10[H3O+]
1 3 5 7 9 11 13
pH = -log10[0.500]
= -(-0.301)
Where do these numbers come from?
∴ pH = 0.301
pH = -log10[H3O+] 2. If the concentration of hydronium ions is
pH is the negative logarithm of the [H3O+] = 0.00252molL-1, what is the pH?
molar concentration of hydronium ions Solution: pH = -log10[H3O+]
= -log10[0.00252]
Notes:
1. You must know that [square brackets] around any = -(-0.2.60)
∴ pH = 2.60 Now Complete
chemical species means “molar concentration”.
Worksheet 4
2. “log10” means the “logarithm to base 10”. This is a 3. If the pH = 3.75, what is [H3O+]?
mathematical function, best understood by example:
Solution pH = -log10[H3O+]
If 100 = 102, then log10(100) = 2
1,000 = 103, then log10(1,000) = 3 so [H3O+] = Inverse(log(-3.75))
500 = 102.699, then log10(500) = 2.699 ∴ [H3O+] = 0.000178 molL-1.
pH values are therefore, powers of 10.
Example:
3. Different calculators may handle log functions Acid “P”: [H3O+] = 10-5molL-1. pH = 5
differently. You must find out or figure out how to do log
Acid “Q”: [H3O+] = 10-3molL-1. pH = 3
functions on your calculator.
Acid “R”: [H3O+] = 10-2molL-1. pH = 2
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and the pH can be expected to be well above the values found for HCl or H2SO4.
By experiment you will have found that a 1 molL-1 CH3COOH solution has a pH ≅ 2.
Self-Ionisation of Water
Water itself can be considered as an extremely weak acid, since in pure water a few water molecules ionise
and donate a proton to another molecule.
2 Water Proton transfer In pure water, at 25oC, it turns out that the
Molecules concentration of hydronium ions,
[H3O+] = 1.00 x 10-7 molL-1.
δ- δ+ δ- δ+
So the pH of pure water:
pH = -log10[H3O+]
= -log10[1.00 x 10-7]
- + = -(-7.00)
∴ pH = 7.00
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A useful way to describe the equilibrium is called Notice that pOH + pH = 14 (at 25oC).
the “Ion-Product” for water.
This means that in a water solution, if the pH is
Kw = [OH-] [H3O+ ] = 1x10-14 at 25oC. (say) 3, then pOH = 14 - 3 = 11
This allows you to calculate the concentration of
hydroxide ions, as well as hydronium ions from pH.
If each part of this expression is manipulated by
taking the negative logarithm (-log), you get
(Mathematical note: In the expression for Kw the
concentrations are multiplied, but this becomes an
pKw = pOH + pH = 14 addition when log functions are applied. This is because
(Note that the lower case “p” in front of an expression logs are index numbers (powers) which must be added
is taken to mean “-log” of that value.) when multiplying expressions.)
Solution (cont.)
Example Calculations: pH and pOH b) pOH + pH = 14, so pH = 14 - pOH
1. In a water solution at 25C, the concentration of = 14 - 4.30
hydroxide ions [OH-] = 5.0 x 10-5 molL-1. = 9.7
c) pH = -log10[H3O ]+
Water is Amphiprotic
Water Can Act as a Base Water Can be an Acid, Too
Previously, we explained the formation of hydronium Water can also act as an acid and donate a proton.
ions in water solution using this example: For example, when ammonia, NH3 dissolves:
HCl(g) H2O(l) Cl-(aq) H3O+(aq) NH3(g) + H2O(l) NH4+(aq) + OH-(aq)
molecule
+ ion
+ ion ion
molecule ion
+ Cl- + +
Acid Base Base Acid
Base Acid Acid Base
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Neutralisation... Again Leaving out the spectators, the net ionic equation
Now that you know about B-L Theory, we can go is...
back to look again at the simple acid-alkali
neutralisation. hydronium + hydroxide water
Example ion ion
hydrochloric + sodium water + sodium
acid hydroxide chloride H3O+(aq) + OH-(aq) 2H2O(l)
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Salts from Acid-Base Neutralisations
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Although we might view all neutralisations as Strong Weak Base
essentially the same reaction and ignore the Base
“spectator ions” which form the “salt”, this prevents e.g. KOH, NaOH e.g. NH3
us noticing a useful pattern which was mentioned
on the previous page.
Strong forms forms
The nature of the “salt” formed depends on whether Acid NEUTRAL salts ACIDIC salts
the acid and base were “strong” or “weak”, as e.g. HCl, e.g. NH4Cl,
shown at right... see the pattern? HNO3, e.g. KCl, NaNO3 NH4NO3
H2SO4 K2SO4 (NH4)2SO4
Why is Ammonia (NH3) a “Weak Base”?
Although there is no water present, and no H3O+ or OH- ions are formed at any time,
this is clearly an acid-base reaction, according to the B-L definition.
Changes in pH When Solutions are Diluted
What happens to the pH of a solution if it is diluted? This is best understood with some worked examples.
Since HCl is a strong acid, then [H3O+] = 0.25 molL-1. pOH = -log10[OH-] = 0.30. Now pOH + pH = 14
pH = -log10[H3O+] ∴ pH = 13.7
= -log10[0.25] b) Can use c1V1 = c2V2, or apply logic:
= -(-0.602) ∴ pH = 0.60 Diluting 1mL to 250mL is a dilution factor of 250.
b) Can use c1V1 = c2V2, or apply logic: ∴ [OH-] will be 250 times lower = 0.5 / 250 = 0.002
Diluting 5mL to 100mL is a dilution factor of 20.
∴ [H3O+] will be 20 times lower = 0.25 / 20 = 0.0125 pOH = -log10[OH-] = 2.70. ∴ pH = 11.3
pH = -log10[H3O+] = -log10[0.0125] (lower pH means less basic)
∴ pH = 1.9 (higher pH means less acidic)
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The purpose of titration is Chemical Analysis. Titration can be used for any reaction for which you
It allows the concentration of an “unknown” solution can determine the “end-point”. Acid-base
to be determined by calculation, after measuring the neutralisations are ideal because indicators (or pH
volume of a known-concentration “standard solution” probes) can identify the end-point.
which reacts with a sample to reach the
“equivalence-point” (end-point). This is the point
where the reactants have been consumed in exactly
Burette
the molar ratio specified by the balanced equation. measures the volume of
“standard solution” needed
Titration Technique to reach the end-point.
• You must have a “standard solution” (next page)
= 2 x 0.04252 x 33.90
Ca, Cb = concentrations (molL-1) of acid & base solns 1 x 25.00
Va, Vb = volumes (mL) of each solution used.
a, b = molar co-efficients (balancing numbers) from = 0.1153
balanced equation for reaction.
∴ Concentration of KOH solution = 0.1153 molL-1.
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Titration Technique (cont.)
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Preparing a Standard Solution Selecting the Indicator
Choosing the best indicator to use is not just a
The key to titration is to have available a suitable
matter of which colour change you’d prefer looking
“standard solution”.
at.
The problem is to get a substance which is of very
Each indicator changes colour over a range of pH
high purity and stability to use as a “Primary
values, and the trick is to choose an indicator which
Standard” to make the solution from.
will change colour as close to the “end-point” as
possible.
The common acids like H2SO4, and bases like
NaOH, cannot be obtained in the pure state due to Colour in Changes
the way they rapidly absorb water and/or CO2 from Indicator Acid Base at pH
the atmosphere.
Litmus red blue 6-8
Suitable primary standard substances are: Bromothymol blue yellow blue 6.2 - 7.6
Methyl orange red yellow 3.1 - 4.4
• Base: anhydrous sodium carbonate, Na2CO3 Phenolphthalein clear pink 8.3 - 10.0
• Acid: oxalic acid, COOHCOOH (diprotic)
Isn’t the end-point always at neutral, pH = 7 ??
Calculate the mass of pure, (I hear you ask)
dry Primary Standard solute
required for solution, and No, its not! Remember (see p.12) that the “salts”
weigh out accurately formed by different combinations of strong or weak
acids and bases may have acidic or basic
properties. This means that, at the exact end point,
the pH might not be neutrality.
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12
pH changes rapidly
with each drop of
base added, so the
end-point can be
10
determined precisely.
Burette adds standard
pH
7
side of neutral, that the choice
of indicator is really not
Strong Acid critical... all indicators will
To start with,
& adding base has
change colour on the same
4
drop of added base.
Strong Base little effect
on pH
2
Titration
end-point
Volume of Base
0
12
Connection to
10
computer or
pH meter The end-point is at pH>7
because the salt is basic...
pH
Weak Acid
7
Flask contains
2
Titration
“unknown” acid end-point
solution Volume of Base Added
0
Weak Acid
Magnetic stirrer pH probe &
10
The end-point is at
pH<7 because the
salt is acidic...
10
must choose
methyl orange, or
4
similar.
The end-point is
theoretically at pH=7 but
2
7
pH
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More About Titration Graphs
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14
All the titration graphs on the previous page were examples of a
titration where the “unknown” solution (in the flask) was an acid.
It was titrated by adding known “standard” base solution from
12
the burette.
Strong Acid
10
You can tell from the graphs, because the pH starts low (acidic) &
and ends high (basic) as it proceeds beyond the end point. Strong Base
pH
7
Look at the graph at right. It begins high (basic) and ends low
(acidic). This means the “unknown” in the flask was a base and
4
acid was added from the burette to move through the end point.
2
You can also look for clues as to whether the acid & base were Titration
“strong” or “weak”. The precise pH depends on concentrations end-point
of solutions, but generally speaking: Volume of Acid
0
• if the “acid end” of the graph begins or ends near ph = 0, then
14
the acid must be strong.
12
then the acid must be weak. Weak Acid
&
10
• if the “base end” of the graph begins or ends near ph = 14, then Strong Base
the base must be strong.
pH
Conductivity Graphs
0
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Dissociation Constants & pKa
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You were previously introduced to the... Perhaps you didn’t realise it then, but this
Ion-Product of Water expression arises from the equilibrium constant for
When pure water undergoes self-ionisation... the dynamic equilibrium.
And, (we are sure you saw this coming!) it is often Ka = [H3O+ ] [CH3COO-]
convenient to take the negative logarithm of this [CH3COOH]
value and call it “pKa”
Since only about 1% of molecules dissociate, you
can figure out that the value of Ka will be much
pKa = -log10(Ka) smaller and pKa very much larger.
In fact, pKa = 4.76
a) Write an equation for its B-L dissociation in a) Write expressions for the dissociation equilibrium
water. and for Ka.
b) Identify the conjugate pairs involved.
c) Write an expression for Ka. b) Find the value for Ka and pKa.
d) Calculate the pH of a 0.200 molL-1 HF solution.
Solution Solution
a) HF + H2O H3O+ + F- a) HA + H2O H3O+ + A-
d) Since pKa = 3.17, then Ka = antilog (-3.17) ∴ Ka = [H3O+ ] [A-] = (3.16x10-5)2 / 0.350
∴ Ka = 6.76 x 10-4 [HA]
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Buffers
keep it simple science
A “Buffer”, or “buffered solution”, is a solution A Natural Buffer System
which can absorb significant amounts of acid or The classic example of a natural buffer system is
base with minimal change in pH. the way our blood is maintained at a pH = 7.4,
despite the fact that we keep exchanging CO2
Biology students will be aware that in all living (acidic), excreting wastes, absorbing foods, etc.
things it is vital that the conditions within the
body/cells are kept very constant. Living things The main chemical buffer in our blood is a solution
cannot function properly if their “internal containing both the bicarbonate ion (HCO3- ) and its
environment” undergoes large changes in: conjugate base, the carbonate ion ( CO32- ).
The fluids inside all living things are buffered, so If the environment is acidic, HCO3- acts as a base:
that pH remains remarkably constant, despite proton transfer
changes in the external environment, eating acidic
food, breathing, excreting, etc, all of which could H3O+(aq) + HCO3-(aq) H2CO3(aq)+ H2O(aq)
alter the body’s pH.
If the environment is basic, HCO3- acts as an acid:
How do Buffers Work?
All buffers are solutions containing a weak acid and its proton transfer
conjugate base.
OH-(aq) + HCO3-(aq) CO32-(aq)+ H2O(aq)
CH3COOH(aq)+ H2O(l) H3O+(aq)+ CH3COO-(aq)
So, the total buffering system can be summarised
weak acid conjugate base
as:
This equilibrium constitutes a buffer solution, so long as - H+ - H+
there are significant amounts of the ethanoate ion H2CO3 HCO3- CO32-
(CH3COO-) present. (e.g. by adding CH3COONa) + H+ + H+
If acid is added (i.e. [H3O+] increases) (pH lower) This system is highly effective at maintaing the pH
then (by Le Chatelier’s Principle) the equilibrium shifts of our blood. Be aware that it is not the only buffer
left, absorbing H3O+ and lowering [H3O+] again. operating.
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