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16.1 The Oldest Theory is the Arrhenius Theory

Arrhenius looked at the substances which were called acids taste sour turn blue litmus to red neutralize bases release hydrogen gas when added to an active metal

release carbon dioxide when added to a carbonate.

and said these properties were due to the production of H+ ions when acids dissolve in water.

Today we know that a bare proton does not exist in water, it forms a chemical bond with a water molecule forming the H3O+. This ion is called the hydronium ion.

Arrhenius looked at the properties of bases.

taste bitter feel slippery (soapy) turn red litmus blue neutralize acids.

Arrhenius said these properties were due to the production of OH- ions when bases are dissolved in water.

NaOH KOH

sodium hydroxide

lye

potassium hydroxide liquid soap stabilizer for plastics

Ba(OH)2 barium hydroxide

Mg(OH)2 magnesium hydroxide MOM Milk of

magnesia
Al(OH)3 aluminum hydroxide Maalox (antacid)

Arrhenius acid is a substance that produces H+ (H3O+) in water

Arrhenius base is a substance that produces OH- in water

Neutralization is

H+ + OH- H2O
or TODAY

H3O+ + OH- 2 H2O

This acid base theory is limited to water solutions. solvent WATER must be the __________ .

Another Acid/Base Definition

Brnsted - Lowry Theory

acid donates a proton in a proton transfer reaction. What is meant by a proton here? A proton is really just a hydrogen atom that has lost its electron!

Accepts a. proton B/L base is the species which _________ general acid - base reaction:

HA(aq) + B(aq)
acid base

HB+(aq)

A-(aq)
conjugate base

conjugate acid

conjugate adj \kn-ji-gt, -j-gt\ Definition of CONJUGATE 1 a : joined together especiall y in pairs : coupled b : acting or operating as if joined 2 a : having features in common but opposite or inverse in some particular b : relating to or being conjugate complex numbers <complex roots occurring in conjugate pairs> 3 of an acid or base : related by the difference of a proton <the acid NH4+ and the base NH3 are conjugate to each

A Brnsted-Lowry acid is a proton donor A Brnsted-Lowry base is a proton acceptor

base

acid

conjugate acid

conjugate base

HClO4 perchloric acid HI HBr HCl H2SO4 HNO3 hydroiodic acid hydrobromic acid hydrochloric acid sulfuric acid nitric acid

Why do we call them strong acids? - They ionize 100%...Ka is large

H2SO4 is special because it is diprotic. There is an equilibrium constant for the removal of the 2nd H+.

Conjugate base Every Brnsted - Lowry acid has a _________________, and every B/L base has a _______________ Conjugate acid

For a specific weak acid reaction:

With a weak acid, we have an equilibrium mixture of all four species. Weak acids do NOT dissociate 100%.

CH3COOH is the

acid _____________________.

base H2O is the _________________________.

H3O+ CH3 is the ____________________. is the _____________________.

Conugate acid

COO-

Conjugate base

For a specific weak base reaction:

base NH3 is the _________________________.

H2O is the _____________________ acid OH-

Conjugate base is the ____________________.

NH4+ is the _____________________. Conjugate acid NH3 is a weak base. There are not many ions in NH3 molecules solution. The strong smell is due to __

What do you notice about water in the above examples?

Amphoteric : A chemical species that behaves both as an acid and as a base is called amphoteric.

LiOH
NaOH KOH Ca(OH)2 Sr(OH)2 Ba(OH) M-O.

A specific strong acid - base reaction:

HCl(aq) + H2O(l) H3O+(aq) + Cl-(aq)

acid HCl(aq) is the ___________________ .

base H2O(l) is the ________________ .

Conjugate acid H3O+(aq) is the ________________________.

Conjugate base Cl-(aq) is the _________________________ .

100% dissociation / good H+ donor equilibrium lies far to right HA H+ + ABefore dissociation After dissociation

Relative # moles HCl H+ Cl-

HCl H+ Cl-

<100% dissociation / not-as-good H+ donor equilibrium lies far to left HA H + + ABefore dissociation After dissociation

Relative # moles HA

H+ A-

HA H+ A-

. Relative Strengths of Acids and Bases (B/L)

A) Strong Acid

No molecules of HA in water solution. B) Weak Acid

An appreciable number of HB molecules exist in water solution. Only a few H3O+ ions and B- ions exist in the solution.

An acid-base reaction normally goes in the direction of the weaker acid. You can use this fact to compare the relative strengths of any two acids. If we have 0.10 M of the following acids, we obtain the following results. For acetic acid:

For hydrofluoric acid:

CH3COOH and HF are __________ acids than H3O+.

weaker

stronger acid than CH3COOH. HF is a __________

In water all the strong acids are essentially 100% ionized. Is HCl stronger , weaker or equal to that of HI? In water they are of equal strength since they both are 100% ionized.

This is known as the leveling effect of water.

. Strong acids form conjugate bases which have no measurable strength in water Within a series of acids, the stronger the acid, the weaker the conjugate base, and the reverse is also true.

weaker the acid the stronger the The _______ ________ base. What does this mean with conjugate respect to these particles in solution?

Acids
Increase strength

Conjugate Bases

Increase strength

pH and the Self Ionization of Water

In any sample of water, there are some ions which result from the dissociation of water itself.

Neutral solution

Kw= 1x 10-14

[H+] > [OH-] are acidic solutions.

[OH-] > [H+] are basic solutions.

You must keep in mind that in water solutions of acids and bases there are always OH- and H3O+ ions due to the self ionization of water.

These ions from water do not add many ions to reasonable concentrations of acid and base solutions, but you must remember that they are there.

Kw at 25 C = [H3O+] [OH-] = (1.0 X 10-7)2 = 1.0 X 10-14

o

If [H3O+] is 1.0 x 10-10 M then what is the [OH-] ?

Kw =

[H3O+]

[OH-]

1.0 X 10-14 = (1.0 X 10-10) [OH-] 1.0 X 10-4 = [OH-]

Log Log Log Log Log Log Log Log

0.1 Mol/L

0.01 M 0.001 M 0.0001 M 0.00001 M 0.000001 M 0.0000001 M

= = = = = = = =

-1
-2 -3
-4

-(-1) = 1 -(-2) = 2 -(-3) = 3

-5 -6 -7 -8

Take our your calculator

The power of the hydrogen pH = - log [H+]

What is the pH of a 0.5 M soln? pH = -log[0.5] = -(-0.301) = 0.301 Find the pH of a 3.8 x 10-4 soln pH = 3.4

The pH of a sample of water is 6.5. Calculate the molarity of the hydrogen ion.

pH = -log[H+] -pH = log [H+] Inverse log = inverse log Inverse log (pH) = [H+] Inverse log (-6.5) = [H+] = 3.16 x 10-7

If the pH of Coke is 3.12, [H+] = ??? pH = - log [H+] - pH = log [H+] Take antilog (10x) of both sides and get

10-pH = [H+]
[H+] = 10-3.12 = 7.6 x 10-4 M
*** to find antilog on your calculator, look for Shift or 2nd function and then the log button

A solution has a pH of 8.5. What is the Molarity of hydrogen ions in the solution? pH = - log [H+] 8.5 = - log [H+]

-8.5 = log [H+]

Antilog -8.5 = antilog (log [H+]) 10-8.5 = [H+] 3.16 X 10-9 = [H+]

Kw =

[H3O+]

[OH-]

1x 10-14 = 1 x 10-7 1 x 10-7 -log (1 x 10-14) = -log [H3O+] + - log [OH-] 14 = 7 7 pKW = pH + pOH

1 x 10-14 =[H3O+] [OH-] 14 = pH + POH

H+
[H+] >[OH-]

H2 O
[H+] =[OH-]

OH[H+] <[OH-]

Acidic solution
pH < 7

Neutral solution
pH = 7

Basic solution

pH > 7

OH-

H +
1 2 Acidic

OH-

H+
3 4 5 6 7 8 Neutral 9 10

11

OH H+
12

13 14 Basic

What is the pH of the 0.0010 M NaOH solution?

[OH-] = 0.0010 (or 1.0 X 10-3 M)

pOH = - log 0.0010 pOH = 3 pH = 14 3 = 11 OR Kw = [H3O+] [OH-] 1 x 10-14 = [H3O+] [ 1.0 X 10-3 ] 1.0 x 10-11 M = [H3O+]

pH = - log (1.0 x 10-11) = 11.00

The pH of rainwater collected in a certain region of the northeastern United States on a particular day was 4.82. What is the H+ ion concentration of the rainwater?

1.51 x 10-5
The OH- ion concentration of a blood sample is 2.5 x 10-7 M. What is the pH of the blood? 7.39

Paper tests like litmus paper and pH paper Put a stirring rod into the solution and stir. Take the stirring rod out, and place a drop of the solution from the end of the stirring rod onto a piece of the paper Read and record the color change. Note what the color indicates. You should only use a small portion of the paper. You can use one piece of paper for several tests.

Tests the voltage of the electrolyte Converts the voltage to pH Very cheap, accurate Must be calibrated with a buffer solution

Indicators are dyes that can be added that will change color in the presence of an acid or base. Some indicators only work in a specific range of pH Once the drops are added, the sample is ruined Some dyes are natural, like radish skin or red cabbage

Copyright by Houghton Mifflin Company. All rights reserved.

57

1. Add solution from the buret. 2. Reagent (base) reacts with compound (acid) in solution in the flask. 3. Indicator shows when exact stoichiometric reaction has occurred. (Acid = Base)

This is called NEUTRALIZATION.

http://users.skynet.be/eddy /titratie.swf

Setup for titrating an acid with a base

http://www.mhhe.com/physsci/che mistry/essentialchemistry/flash/buffe r12.swf

Solutions of a weak conjugate acid-base pair. They are particularly resistant to pH changes, even when strong acid or base is added.

If a small amount of hydroxide is added to an equimolar solution of HF in NaF, for example, the HF reacts with the OH to make F and water.

If acid is added, the F reacts to form HF and water.

The extent of ionization of a weak electrolyte is decreased by adding to the solution a strong electrolyte that has an ion in common with the weak electrolyte.