9.

3 - The Acidic Environment

Section #4
Theories of Acid Structure
Because of the prevalence and importance of acids, they have been used and studied for hundreds of years. Over time, the definitions of acid and base have been refined

Theories of Acid Structure Lavoisier

Antoine Lavoisier, the French Chemist who pioneered very careful, accurate quantitative methods. In the 1780s, Lavoisier noted that non-metal oxides produced acidic solutions. From this he concluded

Acids contain the element Oxygen

The discovery of the acidic compounds of HCl and HCN contradicted this theory.

Theories of Acid Structure Davy

In 1815, Humphrey Davy noted Acids contained Hydrogen, and the Hydrogen is replaced when reacting with a Metal Davy also noted that compounds of metals and oxygen were often basic.

Both the theories of Lavoisier and Davy were observational definitions. That is, the definitions were based upon experimental observation, and didnt attempt any real in-depth explanation of the structure of acids and bases.

Theories of Acid Structure Arrhenius

In 1884 Savante Arrhenius proposed Acids produce H + ions when in solution (aq) and Bases produce OH - ions when in solution (aq) These definitions are the basis of junior high school acids / base study. This definition is restricted to acids and bases where the solvent is water. This theory cannot explain the fact that some compounds create acidic & basic solutions even though they do not contain H+ or OH- ions (eg NH4Cl forms an acidic solution & K2CO3 forms a basic solution more on this later).

Theories of Acid Structure Bronsted & Lowry

In 1923 Johannes Bronsted & Thomas Lowry independently proposed Acids are proton donors and Bases are proton acceptors Example When HCl molecules dissolve in water, a proton moves from the HCl molecule to a water molecule (creating an hydronium ion) HCl(g) + H2O(l) H3O+(aq) + Cl-(aq)

Theories of Acid Structure

Hence, an acid/base reaction can be considered to be a Proton Transfer Reaction.

Example When Ammonia (NH3) gas dissolves in water, a proton moves from the H2O molecule to the ammonia molecule (creating an ammonium ion) + H2O(l) NH4+(aq) + OH-(aq)

NH3(g)

Notice from these two examples, water can act as either and acid or a base, depending on what it is reacting with. This means that water can be either a proton donor or a proton acceptor! Hence water is an example of an Amphiprotic substance (another example is the HCO3- ion, more later)

Theories of Acid Structure

Remember these definitions Amphoteric Substance = able to react chemically as either an acid or a base Amphiprotic Substance = producing and reacting with protons therefore having properties of both an acid and an alkali

Conjugate Acids & Bases

We have already investigated the following reaction NH3(g) + H2O(l) NH4+(aq) + OH-(aq)

In the above example NH3 & NH4+ are Conjugate Pairs.

Theories of Acid Structure

Conjugate Pairs = differ by one proton & are linked Conjugate pairs are used to describe substances that have such similar molecular structures that becomes the other through the gain or loss of a proton. So using re-examining the reaction, we find two conjugate pairs

Pair #1: H2O & OH-

Pair #2: NH3 & NH4+

H2O(l)

NH3(g)

OH-(aq)

NH4+(aq)

Theories of Acid Structure

In summary, an acid-base reaction involves two different conjugate pairs. acid1 Example conjugate pair 1 HCl + NH3 Cl+ NH4+ + base2 base1 + acid2

conjugate pair 2

It would seem relatively obvious that a strong acid would have a very weak conjugate base (and vice versa).

Theories of Acid Structure Relative Strengths of Bronsted & Lowry Acids & Bases
Strong Bronsted & Lowry acids form weak conjugate Bronsted & Lowry bases, and vis versa.

Example HCl(g) Strong Bronsted & Lowry Acid + H2O(l) H3O+(aq) + Cl-(aq)

conjugate pair

Weak Bronsted & Lowry Base

In other words, the HCl donates protons very readily, and the Cl- ion is a very poor acceptor of protons. Hence the forward reaction is favoured, and HCl dissociates readily!

Theories of Acid Structure

Strong Bronsted & Lowry acids form weak conjugate Bronsted & Lowry bases, and vis versa.

Theories of Acid Structure Monoprotic, Diprotic & Triprotic Acids

Different acids will produce differing amounts of H+ ions when they dissociate in water. Hydrochloric Acid (HCl) is an example of a Monoprotic Acid, because it produces one proton (H+) for each HCl molecule. HCl H+ + Cl-

Sulfuric Acid (H2SO4) is an example of a Diprotic Acid, because it produces two protons (H+) for each H2SO4 molecule. H2SO4 HSO4 H+ H+ + + HSO4SO4-

Theories of Acid Structure

Phosphoric Acid (H3PO4) is an example of a Triprotic Acid, because it produces three protons (H+) for each H3PO4 molecule. H3PO4 H2PO4HPO42 H+ H+ H+ + + + H2PO4HPO42PO43-

pH of Salt Solutions
Remember that one of the problems with the Arrhenius theory of acids and bases was its inability to explain why various salt solutions were acidic or basic. The BronstedLowry theory provides an explanation for these observations.

Theories of Acid Structure

We classify salts that form basic solutions as basic salts, and those that form acidic solutions are called acidic salts. The reaction of a salt with water to produce a change in pH is called Hydrolysis. One of the simplest method of determining the nature of a salt (acidic, basic, or neutral) is to examine how the salt can be produced

Strong Acid Weak Acid Strong Acid

+ + +

Strong Base Strong Base Weak Base

Neutral Salt Basic Salt Acidic Salt

+ + +

Water Water Water

Theories of Acid Structure Neutral Salts

Neutral salts do not react with water to any appreciable extent. Consequently, the pH of the water remains unchanged. Salts such as NaCl, K2SO4 and NaNO3 are neutral salts. The salts of weak bases and weak acids may also be neutral if the relative strengths of the acid and base are similar. This is difficult to achieve in practice, and is not on the HSC course.

Theories of Acid Structure Acidic Salts

Remember, acidic salts are the salts of strong acids and weak bases.

Example
possible formation

Ammonium Chloride NH4Cl

HCl + NH3 NH4Cl + H2O

strong acid weak base acidic salt

The ammonium ion acts as a weak BronstedLowry acid when dissolved in water. This equilibrium lies to the right and the hydronium ion is produced. H2O(l) + NH4+(aq) H3O+(aq) + NH3(aq)

Theories of Acid Structure Basic Salts

Remember, basic salts are the salts of weak acids and strong bases.

Example
possible formation

Sodium carbonate Na2CO3

H2CO3 + 2NaOH Na2CO3 + 2H2O

weak acid strong base basic salt

The carbonate ion acts as a strong BronstedLowry base when dissolved in water. This equilibrium lies to the right as the and the hydroxide ion is produced. H2O(l) + CO32-(aq) OH-(aq) + HCO3-(aq)

Theories of Acid Structure Buffers

The fluids within the bodies of living things must be maintained in a narrow pH range in order for our biochemical processes to occur at an optimal rate.

Example The pH of saliva must be maintained in the range 6.4 7.0 or the amylase enzyme (that catalyses the breakdown of carbohydrates) will not function. Gastric Juices (in the stomach) must have a pH around 1.6 in order for enzymes such as pepsin to catalyse the breakdown of proteins into amino acids. Cells in the pancreas secrete pancreatic juice whose pH must be maintained around 8.5 in order for lipase enzymes to digest fats into fatty acids. The alkalinity of this fluid also neutralises gastric juices from the stomach as they enter the small intestine.

Theories of Acid Structure

Solutions called Buffers resist changes in pH when small quantities of an acid or base are added to them. Natural buffers restrict the pH range of body fluids, ensuring that biochemical reactions proceed at their required rate. Buffers are also used in a chemical laboratory to calibrate pH meters, as well as providing a constant pH environment for chemical processes.

How Buffers Work

Buffer solutions usually contain a weak BronstedLowry acid and its conjugate base (or a weak BronstedLowry base and its conjugate acid). By choosing the correct amounts of the weak acid / base (and their conjugates) in the solution, the pH of the solution can be fixed to within narrow limits.

Theories of Acid Structure

Example Consider Acetic Acid in solution CH3COOH(aq)
weak acid 1% dissociation

H2O(l)

H3O+(aq)

CH3COO-(aq)

hence very small amounts of these ions present in solution

So
NaOH HCl

The added OH- ions can be easily neutralised until the CH3COOH is used up thus the pH of the solution slowly becomes basic! The added H3O+ ions cannot be easily neutralised since there is little CH3COOions to react with them thus the pH of the solution becomes more acidic!

C H 3 COOH

Theories of Acid Structure

Example Now consider a solution of Acetic Acid & Sodium Acetate CH3COOH(aq)
present due to original solution of acetic acid

H2O(l)

H3O+(aq)

CH3COO-(aq)

large amount present due to added sodium acetate

So
NaOH HCl

The added OH- ions can be easily neutralised by the CH3COOH The added H3O+ ions can be easily neutralised by the CH3COO- ions

CH 3 C OOH CH 3 C OO
-

Hence the pH of the solution will resist changing because of added acid or base

Theories of Acid Structure Titrations

A Titration is a Volumetric Analysis technique where accurate measurement of volumes are used to deduce the concentrations of unknown solutions. Several basic chemistry skills are required to complete a successful titration, these include 1. Accurate and precise laboratory skills. 2. Balancing Chemical Equations. 3. Mathematical analysis of the results and deduction of the unknown concentration.

Types of Titrations
There are several different type of titrations, however the most common variety of titration used in chemistry is the Acid Base Titration.

Theories of Acid Structure

As the name suggests, this involves the analysis of the reaction of an Acid with a Base (neutralisation reaction). The reaction is allowed to precede to the Equivalence Point. The equivalence point is the theoretical point where the acid and base have completely reacted together in molar ratio quantities (given by the balanced chemical equation for the reaction).

Example HCl(aq) + NaOH(aq) NaCl(aq) + H2O(l) The equivalence point of the above reaction occurs when HCl and NaOH have reacted in a 1:1 mole ratio. H2SO4(aq) + 2NaOH(aq) Na2SO4(aq) + H2O(l)

The equivalence point of the above reaction occurs when H2SO4 and NaOH have reacted in a 1:2 mole ratio.

Theories of Acid Structure

When the equivalence point is reached, the solutions pH will depend upon the nature of the reactants.

Example Strong Acid Strong Acid Weak Acid + + + Strong Base Weak Base Strong Base Neutral Salt Solution Acidic Salt Solution Basic Salt Solution pH about 7 pH below 7 pH above 7

If an Indicator is used during a titration, its colour change will signal that the reaction has reached the equivalence point. The point where the indicator changes colour is called the End Point. An indicator is chosen so that its end point will coincide with the expected equivalence point of the neutralisation reaction.

Theories of Acid Structure Preparation & Use of Glassware

The most common equipment used to complete a titration are 1. Burettes

Rinse the internal surface with 10-15mL of the solution that you intent to use (holding the burette almost horizontal). Run this washing liquid through the tap to remove it. Repeat the process if necessary, & discard the washings. Place some of the solution to be used in the burette and run some liquid through the tap for a few seconds to remove any air bubbles. Fill the burette to the top line, using a filter funnel, and remove the funnel when full. Make sure the burette is positioned vertically.

Theories of Acid Structure

2. Pipettes

NEVER pipette by mouth. Rinse the internal surface with 5-10mL of the solution that you intent to use & discard the washings. When filling, do not allow the solution to enter the pipette filler etc When full, hold vertically and check Bottom of meniscus sits on the line No air bubbles are present Drain the liquid into a prepared conical flask, holding the tip of the pipette against the inner surface of the conical flask.

3. Conical Flask

Wash with water. Following a titration, empty & rinse, then it can be used in another titration.

Theories of Acid Structure

4. Volumetric Flask In summary

Used if making standard solutions, or completing dilutions. Rinse the internal surface with water. All solid (for standard solutions) should be dissolved before filling the flask to the line with water. Add the final amounts of water drop by drop. Stopper, invert and mix well.

Wash with water, dont dry

rinse with solution

Theories of Acid Structure Standard Solutions

In general, chemists call a solution of known concentration a Standard Solution. In general, the standard substance that is dissolved should 1. Be a water soluble solid obviously it is easier to measure an accurate amounts of a solid than liquid or gas. 2. Have an accurately known chemical formula mixture are therefore not used. 3. Be stable in air we do not want our chosen chemical to be reacting and changing before or during the weighing process. 4. Have a very high purity analytical reagent (AR) grade or laboratory reagent (LR) grade .

Theories of Acid Structure

The water that is used to dissolve the standard substance should be of the highest purity possible distilled, deionised, demineralised, triply ionised water, etc

Making a Standard Solutions

The following steps are used to create a standard solution 1. Determine the required Concentration and Volume for the standard solution (volume limited to size of volumetric flasks, 100mL, 250mL ). 2. Calculate the number of mole of the substance that is required. 3. Calculate the mass of the substance that is required. 4. Accurately weigh the required mass. 5. Dissolve ALL of the measured mass using pure water, and transfer this to a clean & prepared volumetric flask.

Theories of Acid Structure

6. Fill the volumetric flask to the indicated line. 7. Stopper the flask and mix (invert, rotate, shake ). 8. Calculate the approximate concentration using actual measured mass 9. Label flask with solution details (chemical, date, etc). Example A chemist wished to create 250mL of 0.125M NaOH solution #mol NaOH = 0.125 0.25 = 3.125 10-2 mass NaOH = 3.125 10-2 39.998 = 1.2499g
1.2499 gram of NaOH should be accurately measured out and dissolved in pure water

Theories of Acid Structure Diluting Solutions

Sometimes we may have a solution of known concentration, that we will use to create an new solution of a desired concentration. We often use the cv method, that is we use the following formula C1V1 = C2V2

Example A chemist wished to dilute some of a 5M solution of sulfuric acid, to make 250mL of 1.5M solution of sulfuric acid. solution 1 (original solution) C1 = 5M V1 = ? solution 2 (new solution) C2 = 1.5M V2 = 0.25L C1V1 = C2V2 5 V1 = 1.5 0.25 V1 = (1.5 0.25) 5 V1 = 0.075L V 1 = 75mL
75mL of the original solution can be diluted with pure water in a 250mL volumetric flask to make a 1.5M solution!!

Theories of Acid Structure Titration Methodology

The strategy that is employed during a titration is as follows 1. An accurately known volume of a solution whose concentration is unknown is placed in a conical flask using a Pipette.

unknown concentration

accurately known volume

Theories of Acid Structure

2. A solution of accurately known concentration is placed in a Burette.

accurately known concentration

3. Equipment is setup and an appropriate Indicator is added to the conical flask.

Theories of Acid Structure

4. The solution from the burette is run into the conical flask (while it is swirled to mix completely). 5. When the indicator reaches its End Point (colour change), the volume of solution added from the burette is noted.

Remember at the end point, the acid and base have reacted in mole ratios. Hence we can deduce the unknown concentration of the solution in the conical flask.

Theories of Acid Structure Titration Mathematics

The general equation occurring in a titration is as follows Acid + Base Salt + Water

Since the acid and base used in a titration are both aqueous solutions, the most common properties that we will measure are Concentration and Volume. Also during most titrations, the products (salt & water) are often ignored, it is therefore the Acidic and Basic concentrations and volumes that are the most important. # mol Acid # mol Base

mol ratio

Volume (acid)

[Acid]

Volume (base)

[Base]

Theories of Acid Structure

Example A student prepares a solution of hydrochloric acid that is approximately 0.1M and wishes to determine its precise concentration. A 25.00mL portion of the HCl solution is transferred to a conical flask, and after a few drops of indicator is added, the HCl solution is titrated with 0.0775M NaOH solution. The titration requires exactly 37.46mL of the standard NaOH solution. What is the molarity of the HCl solution? HCl(aq) + NaOH(aq) NaCl(aq) + H2O(l)

# mol NaOH = 0.0775 0.03746 from the equation

= 2.90 10 -3 mol # mol HCl = 2.90 10-3

NaOH : HCl 1 : 1

[HCl] = 2.90 10-3 0.025 = 0.116 M

(mol L-1)