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Chapter-3

AcidBase Equilibria

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Solutions of a Weak Acid or Base

The simplest acidbase equilibria are those in which a weak acid or a weak
base reacts with water.
We can write an acid equilibrium reaction for the generic acid, HA.

HA(aq) + H2O(l)

H3O+(aq) + A(aq)

Acetic acid is a weak acid. It reacts with water as follows:

HC2H3O2(aq) + H2O(l)

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H3O+(aq) + C2H3O2(aq)

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The equilibrium constant for the reaction of a weak acid with water is called the
acidionization constant (or aciddissociation constant), Ka.

[H O ][A ]
=
+

Ka

[HA]

Liquid water is not included in the equilibrium constant expression.

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Concept Check 16.1


You have prepared dilute solutions of equal molar concentrations of HC2H3O2
(acetic acid), HNO2, HF, and HCN. Rank the solutions from the highest pH to the
lowest pH. (Refer to Table 16.1.)
In order of decreasing Ka:

Highest pH

Ka

6.8
HF
HNO2
HC2H3O2
HCN

4.5

10

HCN
HC2H3O2

1.7
4.9

10
10

HNO2

10

HF

10

Lowest pH

A large Ka value indicates a stronger acid (more of the acid dissociates) and
small Ka value indicates a weaker acid (less of the acid dissociates).

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Calculations with Ka
Given the value of Ka and the initial concentration of HA, you can calculate the
equilibrium concentration of all species.
Given the value of Ka and the initial concentration of HA, you can calculate the
degree of ionization and the percent ionization.
Given the pH of the final solution and the initial concentration of HA, you can
find the value of Ka and the percent ionization.
We can be given pH, percent or degree ionization, initial concentration, and
Ka.
From pH, we can find [H3O+].
From percent or degree ionization, we can find Ka.
Using what is given, we can find the other quantities.
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Sorethroat medications sometimes contain the weak acid phenol, HC6H5O. A


0.10 M solution of phenol has a pH of 5.43 at 25 C.

a. What is the acidionization


constant, Ka, for phenol at 25 C?

b. What is the degree of ionization?

HC6H5O(aq) +
Initial
Change
Equilibrium

H3O+(aq) +

H2O(l)

0.10
x
0.10 x

C6H5O(aq)

0
+x
x

We were told that pH = 5.43. That allows us to find [H3O+] = 3.7


M = x = [C6H5O].

0
+x
x

10

Now we find [HC6H5O] = 0.10 x = 0.10 M.


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Finally, we write the expression for Ka and substitute the concentrations we now
know.

H3O+ + C6H5O

HC6H5O + H2O

[H3O+] = [C6H5O] = 3.7 106 M


[HC6H5O] = 0.10 M

[H O ] [C H O ]
=
+

Ka

[HC 6H5 O]

(3.7 10 6 )2
Ka =
0.10
Ka = 1.4 1010
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The degree of ionization is the ratio of ionized concentration to original


concentration:

3.7 106
x
Degree of ionization =
=
0.10
0.10
Degree of ionization = 3.7 105
Percent ionization is the degree of ionization 100%:
Percent ionization = 3.7 103% or 0.0037%
Simplifying Assumption for Acid and Base Ionizations
The equilibrium concentration of the acid is most often ([HA]0 x).
If x is much, much less than [HA]0, we can assume that subtracting x
makes no difference to [HA]:
([HA]0 x) = [HA]0
This is a valid assumption when the ratio of [HA]0 to Ka is > 103.
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Parahydroxybenzoic acid is used to make certain dyes. What are the


concentrations of this acid, of hydronium ion, and of parahydroxybenzoate ion
in a 0.200 M aqueous solution at 25 C? What is the pH of the solution and the
degree of ionization of the acid? The Ka of this acid is 2.6
105.

We will use the generic formula HA for parahydroxybenzoic acid and the following
equilibrium:
HA + H2O
H3O+ + A

Initial

HA(aq) +
0.200

Change
Equilibrium

x
0.200 x

[H O ][A ]
=
[HA ]
+

Ka

H3O+(aq) + A(aq)
0
0

H2O(l)

+x
x

2.6 10

+x
x

x2
=
0.200 x

0.200
> 1000, so 0.200 x 0.200
2.6 105
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Ka =

x2
0.200

5.2 10 6 = x 2
x = 2.3 10 3 = [H3 O + ]

pH = log [H3O+ ] = log (2.3 103 )


pH = 2.64

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Polyprotic Acids
A polyprotic acid has more than one acidic protonfor example, H2SO4,
H2SO3, H2CO3, H3PO4.
These acids have successive ionization reactions with Ka1, Ka2, . . .
The next example illustrates how to do calculations for a polyprotic acid.
Tartaric acid, H2C4H4O6, is a diprotic acid used in food products.
What is the pH of a 0.10 M solution?
What is the concentration of the C4H4O62 ion in the same solution?
Ka1 = 9.2 104; Ka2 = 4.3 105.

First, we will use the first acidionization equilibrium to find [H+] and
[HC4H4O6]. In these calculations, we will use the generic formula H2A for the
acid.
Next, we will use the second acidionization equilibrium to find [C4H4O62].
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H2A(aq) +
Initial

+x

+x

0.10 x

[H O ][HA ]
=
+

K a1

HA(aq)

0.10

Change
Equilibrium

H3O+(aq) +

H2O(l)

[H2 A ]

9.2 10

x2
=
0.10 - x

0.10
< 1000
9.2 10 4
We cannot use the simplifyin g assumption .

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9.2 10 4 (0.10 x ) = x 2
9.2 10 5 9.2 10 4 x = x 2
x 2 + 9.2 104 x 9.2 105 = 0

a =1

b = 9.2 104
x=

c = 9.2 105

b b 2 4ac
2a

(9.2 104 ) (9.2 104 )2 4(1)( 9.2 105 )


x=
2(1)

(9.2 10 4 ) (1.92 10 2 )
x=
= 4.6 10 4 9.6 10 3
2
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x = 9.1 103

and

x = 1.0 102

We eliminate the negative value because it is


physically impossible to have a negative
concentration.
At the end of the first acid ionization equilibrium,
the concentrations are
[H3O+] = 9.1 103 M
[HA] = 9.1 103 M
[H2A] = 9.0 104 M
Now we use these for the second acidionization
equilibrium.
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HA(aq) +
Initial
Change
Equilibrium

Ka2

0.0091

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H2O(l)

H3O+(aq)
+
0.0091

A2(aq)
0

+x

+x

0.0091 x

0.0091 + x

H3O+ A 2
=
HA

4.3 105 =

(0.0091 + x )x
(0.0091 x )

We can assume that


0.0091 + x 0.0091 and 0.0091 x 0.0091
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4.3 10 5 =

0.0091 x
0.0091

x = 4.3 10 5 M
Our assumption was valid.

[C4H4O62 ] = 4.3 105 M


[HC4H4O6 ] = 9.1 103 M
[H3O + ] = 9.1 10 3 M
[H2C 4H4O 6 ] = 9.0 10 4 M
pH = log (9.1 10 3 )

pH = 2.04

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BaseIonization Equilibrium
The simplest acidbase equilibria are those in which a weak acid
or a weak base reacts with water.
We can write a base equilibrium reaction for the generic base, B.
B(aq) + H2O(l)
HB+(aq) + OH(aq)
Ammonia is a weak base. It reacts with water as follows:
NH3(aq) + H2O(l)

NH4+(aq) + OH(aq)

Here the generic B from the previous slide is NH3(aq).


The equilibrium constant for the reaction of a weak base with water is called the
baseionization constant, Kb.
+

Kb =

[HB ][OH ]
[B]

Liquid water is not included in the equilibrium constant expression.


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Writing Kb Reactions
The bases in Table 16.2 are nitrogen bases; that is, the proton they accept
adds to a nitrogen atom. Next well practice writing the Kb reactions.
Ammonium becomes ammonium ion:
NH3+ H2O NH4+ + OH
Ethylamine becomes ethyl ammonium ion:
C2H5NH2 + H2O C2H5NH3+ + OH

Dimethylamine becomes dimethylammonium ion:


(CH3)2NH2 + H2O (CH3)2NH3+ + OH
Pyridine becomes pyridinium ion:
C5H5N+ H2O C5H5NH+ + OH
Hydrazine becomes hydrazinium ion:
N2H4+ H2O N2H5+ + OH
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10

We can be given pH, initial concentration, and Kb.


From the pH, we can find first [H3O+] and then
[OH]. Using what is given, we can find the other quantities.
We can also use a simplifying assumption: When [B]0 / Kb > 103, the
expression ([B]0 x) = [B]0.

Aniline, C6H5NH2, is used in the manufacture of some


perfumes. What is the pH of a 0.035 M solution of aniline at
25C? Kb= 4.2 1010 at 25C.

We will construct a chart and solve for x.


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C6H5NH2(aq)
+
Initial
Change
Equilibrium

C6H5NH3+(aq) + OH(aq)

H2O(l)

0.035
x
0.035 x

0
+x
x

0
+x
x

We are told that Kb = 4.2 1010. That allows us to substitute


into the Kb expression to solve for x.
C6H5NH3+ + OH

C6H5NH2 + H2O

[B] = 0.200 x and [B+] = [OH] = x

[C H NH ][OH ]
+

Kb =

[C 6H5N]

4.2 1010 =

x2
(0.200 x )

0 .2 0 0
> 1 0 0 0 , s o w e c a n a s s u m e th a t 0 .2 0 0 x = x
4 .2 1 0 1 0
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11

4.2 1010 =

x2
0.200

x 2 = 8.4 1011

x = 9.2 106 M

The question asks for the pH:

pH = 14.00 = pOH = 14.00 log [OH ]


pH = 14.00 log (9.2 106 )
pH = 14.00 5.04
pH = 8.96

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Salt Solutions
We will look at the cation and the anion separately, and then
combine the result to determine whether the solution is acidic,
basic, or neutral.

The conjugate acid of a strong base is very weak and does not
react with water. It is therefore considered to be neutral.
Na+ + H2O No Reaction (NR)
The conjugate base of a strong acid is very weak and does not
react with water. It is therefore considered to be neutral.
Cl + H2O NR

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12

The conjugate acid of a weak base reacts with water to form an


acidic solution:
NH4+ + H2O NH3 + H3O+
The conjugate base of a weak acid reacts with water to form a
basic solution:
F + H2O HF + OH
We classify each salt by examining its cation and its anion, and
then combining the result.
NaBr
Na+ is the conjugate acid of NaOH, a strong base. It does not
react with water, so it is neutral.
Br is the conjugate base of HBr, a strong acid. It does not react
with water, so is neutral.
The cation is neutral; the anion is neutral.
NaBr is neutral.
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NaC2H3O2
Na+ is the conjugate acid of NaOH, a strong base. It does not
react with water, so it is neutral.
C2H3O2 is the conjugate base of HC2H3O2, a weak acid. It reacts
with water to give a basic solution.
The cation is neutral; the anion is basic.
NaC2H3O2 is basic.
NH4Cl
NH4+ is the conjugate acid of NH3, a weak base. It reacts with water to give
an acidic solution.
Cl is the conjugate base of HCl, a strong acid. It does not react with water,
so it is neutral.
The cation is acidic; the anion is neutral.
NH4Cl is acidic.
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13

NH4F
NH4+ is the conjugate acid of NH3, a weak base. It reacts with
water to give an acidic solution.
F is the conjugate base of HF, a weak acid. It does not react with
water, so it is basic.
The cation is acidic; the anion is basic. We need more information
in this case. We compare Ka for HF to Kb for NH3.

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If Ka > Kb, the solution is acidic. If Ka < Kb, the


solution is basic. If Ka = Kb, the solution is neutral.

K w 1.0 10 14
For NH4 : K a =
=
= 5.6 10 10
5
K b 1.8 10
+

K w 1.0 10 14
For F : K b =
=
= 1.5 10 11
4
K a 6.8 10

K a for NH 4 > K b for F

NH4F is acidic.
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14

Ammonium nitrate, NH4NO3, is administered as an intravenous solution to


patients whose blood pH has deviated from the normal value of 7.40.

Would this substance be used for acidosis (blood pH < 7.40) or alkalosis (blood
pH > 7.40)?
NH4+ is the conjugate acid of a NH3, a weak base. NH4+ is acidic.

NO3 is the conjugate base of HNO3, a strong acid. NO3 is neutral.


NH4NO3 is acidic, so it could be used for alkalosis.

The hydrolysis equilibrium constant can be used in problems to


determine the pH of a salt solution. To use the hydrolysis
equilibrium, we need to compute the K value for it.

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We can determine K for the reaction of the ion with


water (hydrolysis reaction).
NH4+ + H2O <==> NH3 + H3O+
is the sum of
NH4+ + OH <==> NH3 + H2O K1 = 1/Kb
2H2O <==> H3O+ + OH K2 = Kw
Overall reaction
NH4+ + H2O <==> NH3 + H3O+
K a = K1 K 2 =
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Kw
Kb
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15

What is Kb for the F ion, the ion added to the public water supply
to protect teeth?
For HF, Ka = 6.8 104.

F + H2O <==> HF + OH

Is the sum of
H3O+ + F <==> HF + H2O; K1 = 1/Ka
2H2O <==> H3O+ + OH; K2 = Kw
Overall reaction:
F + H2O <==> HF + OH
K w 1.0 10 14
K b = K1 K 2 =
=
K a 6.8 10 -10

For F- : Kb = 1.5 105


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Household bleach is a 5% solution of sodium hypochlorite, NaClO. This


corresponds to a molar concentration of about 0.70 M NaClO.
What is the [OH] and the pH of the solution?
For HClO, Ka = 3.5
108.

ClO(aq) +
Initial
Change
Equilibrium

HClO(aq) +

OH(aq)

0.70

+x

+x

0.70 x

H2O(l)

We are told that Ka = 3.5 108. That means that Kb= 2.9 107.
This allows us to substitute into the Kb expression to solve for x.
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16

ClO + H2O

HClO + OH

[H3O+] = [A] = x and [HA] = 0.200 x

Kb =

0.70
2.9 107

[HClO] OH

ClO
x2
7
2.9 10 =
(0.70 x )
> 1000, so we can assume that 070 x = 0.70.
x2
7
2.9 10 =
0.70
x 2 = 2.0 10 -7

x = 4.5 10 -4 M
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The question asks for [OH] and the pH:

[OH ] = x = 4.5 104 M


pH = 14.00 = pOH = 14.00 log [OH ]
pH = 14.00 log (4.5 104 )
pH = 14.00 3.35
pH = 10 .65
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17

CommonIon Effect
The commonion effect is the shift in an ionic equilibrium caused by the
addition of a solute that takes part in the equilibrium.
Buffers
A buffer solution is characterized by the ability to resist changes in pH when
limited amounts of acid or base are added to it.
A buffer is made by combining a weak acid with its conjugate base or a
weak base with its conjugate acid.
What is the pH of a buffer made by mixing 1.00 L of 0.020 M benzoic acid,
HC7H5O2, with 3.00 L of 0.060 M sodium benzoate, NaC7H5O2? Ka for benzoic
acid is 6.3 105.
This problem involves dilution first. Once we know the concentrations of
benzoic acid and benzoate ion, we can use the acid equilibrium to solve for x.
We will use HBz to represent benzoic acid and Bz to represent benzoate ion.
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[HBz] =

(0.020 M)(1.0 L)
= 0.0050 M
(1.0 + 3.0) L

[Bz ] =

(0.060 M)(3.0 L)
= 0.045 M
(1.0 + 3.0) L

Initial
Change
Equilibrium

HBz(aq) + H2O(l)
0.0050

H3O+(aq) + Bz(aq)
0
0.045

+x

+x

0.0050 x

0.045 + x

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18

H3O+ Bz
Ka =
[HBz]
x (0.045 + x )
6.3 105 =
(0.0050 x )
We can assume that
0.045 + x 0.045 and 0.0050 x 0.0050
0.045 x
6.3 10 5 =
0.0050
x = 7.0 10 6 M
Our assumption was valid.
[H3O + ] = x = 7.0 10 6 M

pH = log [H3O + ] = log (7.0 10 6 )


pH = 5.15

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Calculate the pH of a 0.10 M HF solution to which sufficient sodium fluoride has been
added to make the concentration 0.20 M NaF. Ka for HF is 6.8 104.

We will use the acid equilibrium for HF.


NaF provides the conjugate base, F, so
[F ] = 0.20 M

[HF] = 0.10 M

H2O(l)

HF(aq) +
Initial
Change
Equilibrium

Ka =

[H3O+ ] [F ]
[HF]

[F] = 0.20 M.

H3O+(aq) +

F(aq)

0.10

0.20

+x

+x

0.10 x

0.20 + x

6.8 10 4 =

We can assume that


0.20 + x 0.20 and
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x (0.20 + x )
(0.10 - x )

0.10 x 0.10
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19

6.8 10 4 =

0.20x
0.10

x = 3.4 10 4 M
Our assumption was valid.

[H3O + ] = x = 3.4 10 4 M
pH = log [H3O + ] = log (3.4 10 4 )
pH = 3.47

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HendersonHasselbalch Equation
Buffers at a specific pH can be prepared using the
HendersonHasselbalch Equation.
Buffers are prepared from a conjugate acidbase pair in which the
ionization is approximately equal to the desired H3O+
concentration.
Consider a buffer made up of a weak acid HA
and its conjugate base A:
HA(aq) + H2O(l) H3O+(aq) + A(aq)
The acidionization constant is
Rearranging to solve for [H3O+]

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Ka =

[H3O + ][A ]
[HA]

[HA]
[H3O+ ] = Ka
[A ]
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20

The preceding equation can be used to derive an equation for the


pH of the buffer.
First, we take the negative logarithm of both sides of the
equation.

[HA]
log[H3O + ] = log K a x
[A ]

[HA]
log[H3O+ ] = log Ka log
[A ]

The pKa of a weak acid is defined in a manner similar to pH


and pOH
pKa = log Ka
We can now express the equation as

This is equivalent to
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[HA]
pH = pKa log
[A ]
[A ]

pH = pK a + log
[HA]
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This equation is generally shown as:

pH = pK a + log

[base]
[acid]

This equation relates buffer pH for different


concentrations of conjugate acid and base and is known
as the HendersonHasselbalch equation.

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21

What is the [H3O+] for a buffer solution


that is 0.250 M in acid and 0.600 M in
the corresponding salt if the weak acid
Ka = 5.80 x 107?

Use as example the following equation of a


conjugate acidbase pair.
HA(aq) + H2O(l)

H3O+(aq) + A(aq)

First, we use the value of Ka to find pKa:


pKa = log(5.80 x 107)
pKa = (6.237)
pKa = 6.237
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pH = pK a + log

16 | 43

[base]
[acid]

pKa = 6.237
[base] = 0.600 M
[acid] = 0.250 M
Substituting:

pH = 6.237 + log

[0.600]
[0.250]

pH = 6.237 + log 2.40


pH = 6.237 + 0.380
pH = 6.617
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22

Using the pH, we can now find [H3O+]:


[H3O+] = 10pH
[H3O+] = 106.617
[H3O+] = 2.42 107 M
AcidBase Titration
An acidbase titration is a procedure for determining the amount
of acid (or base) in a solution by determining the volume of base
(or acid) of known concentration that will completely react with it.
An acidbase titration curve is a plot of the pH of a solution of
acid (or base) against the volume of added base (or acid).
Such curves are used to gain insight into the titration process.
You can use the titration curve to choose an indicator that will
show when the titration is complete.
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This titration plot shows the titration of a strong


acid with a strong base. Note that the pH at the
equivalence point is 7.0.

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23

The equivalence point is the point in a titration when a


stoichiometric amount of reactant has been added.
The indicator must change color near the pH at the equivalence
point.
When solving problems in which an acid reacts with a base, we
first need to determine the limiting reactant. This requires that we
use moles in the calculation.
The next step is to review what remains at the end of the
reaction. In the case of a strong acid and a strong base, the
solution is neutral.
When a weak acid or weak base is involved, the product is a salt.
After finding the salt concentration, we use a hydrolysis
equilibrium to find the pH.

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