EXPERIMENT 4: TITRIMETRIC ANALYSIS Requirements for Titration:

- Known Identity of the Titrant and Analyte

Analytical Chemistry: Branch of Chemistry concerned with the quantitation of analytes - Accurately Determined Concentration of the Titrant
Analyte: Chemical Species whose identity is known but their concentration is unknown. - Known Reaction between the Titrant and Analyte
- Fast Reaction between the Titrant and Analyte
We want the most accurate quantitation of Analytes. We perform accurate mass and
volume measurements to get accurate results as well.
Where do we cease titrating? at the EQUIVALENCE POINT
Analyte in this Experiment: H+ ion. Measured in terms of Molarity [H+] or pH = -log[H+] At the equivalence point, all analyte has been consumed and can be fully accounted on the
Source: CH3COOH (Acetic Acid) – in Vinegar calculations.
H2CO3 (Carbonic Acid) – in Soda. @ the equivalence point: moles analyte = moles titrant.
There are many types of titration, for all the common feature is:
You do not want to stop pre-equivalence point because some there are still unreacted and
the reaction of a titrant (something whose quantity is much known) with an analyte. This is unaccounted H+ there.
the definition of Titration.
You do not want to go past the equivalence point (overtitrated) because you seem to be
Titrant + Analyte 
titrating more H+ when in fact you are just adding excess OH- titrant.
OH- H+  H2O
Known Unknown
The problem however lies in the fact that the transformation OH- + H+  H2O
In the experiment what we did is acid-base titration. Since our analyte is acidic or has acid has no physical manifestations. An indicator is needed to identify the endpoint.
base properties.
Visual Indicators possess the following criteria:
They say titration is Practical/ Experimental Stoichiometry because it involves reacting and 1.) Conjugated Structure (Alternating Single Double Bonds, requirement to resonate absorbed light)
2.) Acid-Base Properties (Can have an Acidic H or not depending whether or not H+ or OH- is in
relating the known titrant to determine the unknown analyte.
excess.
Titrimeric Analysis is a Volumetric Method and offers the advantage of:
(1) Fast Reaction, better collission among reactants.
(2) Reproducible Results since solutions are homogeneous (unlike solid phase reactions)
(3) Controllable Reaction (through stirring)
3.) Different Lewis Structure or Extent of Resonance in Acidic and Basic

CHEM 16: GENERAL CHEMISTRY I LABORATORY EXPERIMENT 4 POST LAB DISCUSSION MOLINO, R. J. E.
Example: Phenolpthalein Indicator. Prior to Unknown Quantitation, Standardization needs to be done.
Since we are a bit uncertain of the concentration of our Titrant.

Standardization carried out in the experiment:

PH- + OH-  P2- + H 2O
(from KHP, primary (Titrant,
standard, CERTAIN) UNCERTAIN)

KHP has an acidic H and can react with a base (acid base titration and phenolphthalein
The indicator has acid-base property (has an acidic H) and therefore is added in small indicator can be done similarly)
amounts so that it will not be titrated and affected the determined pH of the samples.
The exact concentration of the titrant is determinable from the amount of primary standard
The indicator is added in small amounts and serve the purpose of detecting whether H+ or it reacted with.
OH- is in excess in its surrounding.
e.g. Pre-Equivalence Point: H+ is in excess. Traces of pink will appear as incoming OH- Characteristics of a Primary Standard (Also a reason why NaOH is not a primary standard by
droplets are detected. But all OH- will soon be consumed by an excess H+ and color after itself)
swirling is colorless 1.) High and Known Purity
Post-Equivalence Point: OH- is in excess. Overtitrated Solution is dark pink. 2.) High Molecular Weight
3.) Known, Fast, and Single Reaction with the Titrant
The Indicator actually changes color at a pH unique from the equivalence point. The pH 4.) Stable in Air, Nonhygroscopic (does not readily absorb moisture) Thermally Stable
where the indicator changes is called the ENDPOINT.
We choose the indicator such that the ENDPOINT is near the EQUIVALENCE POINT. Relevant Formulas for the Data Treatment:
We want Equivalence Point = Endpoint or Standardization: PH- + OH-  P2- + H 2O
Endpoint slightly pass the Equivalence Point 𝑔 𝑝𝑢𝑟𝑒 𝐾𝐻𝑃 𝑚𝑜𝑙 𝐾𝐻𝑃 𝑚𝑜𝑙 𝑁𝑎𝑂𝐻
𝑚𝑜𝑙 𝑁𝑎𝑂𝐻 (___ 𝑔𝐾𝐻𝑃)(0.𝑥𝑥𝑥𝑥 )( )( )
𝑔 𝐾𝐻𝑃 𝑤𝑒𝑖𝑔ℎ𝑒𝑑 204.22 𝑔 𝐾𝐻𝑃 𝑚𝑜𝑙 𝐾𝐻𝑃
But never, Endpoint right before the Equivalence Point because then not all analyte is [NaOH] = = 𝐿
𝐿 𝑁𝑎𝑂𝐻 (𝑉𝑓−𝑉𝑜)𝑚𝐿 𝑁𝑎𝑂𝐻 𝑖𝑛 𝑏𝑢𝑟𝑒𝑡𝑡𝑒 𝑥
1000 𝑚𝐿
reacted and detected.
- We start with our known, g of the primary standard KHP.
- We look for what we are targeting in the denominator. L NaOH. NaOH our titrant is
located in the burette so we indicate our volume measurement there.
- No need to multiply the expression to an aliquot factor since we did NO DILUTION of
our NaOH titrant during titration.

CHEM 16: GENERAL CHEMISTRY I LABORATORY EXPERIMENT 4 POST LAB DISCUSSION MOLINO, R. J. E.
Unknown Quantitation: ERROR ANALYSIS:
We have to be aware, are we seeking to quantify [H2CO3], [H+] or pH? A systematic approach in solving Error Analysis problem involve:
1.) Identification of the Error
2.) Determining when the Error was Committed
Formula for pH = -log [H+] 3.) Point out the parameter whose response to the error is asked.
Because of the negative logarithm, the relationship between pH and [H+] 4.) Look at the formula for that parameter/ quantity. It will be more efficient if Error Analysis is done in terms
is an inverse one. of formulas rather than qualitatively although conceptual analysis can be used to double check.
𝑚𝑚𝑜𝑙 𝑁𝑎𝑂𝐻 𝑚𝑚𝑜𝑙 𝐻+
𝑚𝑚𝑜𝑙 𝐻 + (𝑉𝑓−𝑉𝑜)𝑚𝐿 𝑁𝑎𝑂𝐻 𝑡𝑖𝑡𝑟𝑎𝑛𝑡 ( )( ) 70𝑚𝐿 𝑝𝑟𝑒𝑠𝑒𝑛𝑡 𝑣𝑜𝑙𝑢𝑚𝑒
[H+] = = 𝑚𝐿 𝑁𝑎𝑂𝐻 𝑡𝑖𝑡𝑟𝑎𝑛𝑡 𝑚𝑚𝑜𝑙 𝑁𝑎𝑂𝐻
𝑥 Example:
𝑚𝐿 𝐻 + 𝑚𝐿 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 (𝑖𝑛 𝑡ℎ𝑒 𝑒𝑥𝑝𝑡 50+20 𝑚𝐿) 20 𝑚𝐿 𝑎𝑐𝑡𝑢𝑎𝑙 𝑠𝑎𝑚𝑝𝑙𝑒
1.) Overtitration. Standardization. Effect on [NaOH]
- Starts with the knowns, the now determined concentration of the titrant as well as Formula: Referring to the formula for [NaOH] overtitration or increase in the delivered volume of the
titrant will cause an increase in the denominator and a lower [NaOH] ↑VNaOH ↓[NaOH] DECREASE
the volume of the titrant added. Conceptual: It will appear that the [NaOH] is lower since you need more of it to neutralize the
- We only put the volume of the solution we are titrating on the denominator. We do weighed amount of KHP when in fact, you just put an excess of NaOH and all KHP has been
not include the volume of the titrant we delivered (titrant also has no H+) neutralized already.
- There is a need to multiply the expression to an appropriate dilution factor (in this 2.) Overtitration. Unknown Analysis. Effect on [H+].
Formula: For the Unknown Quantitation of H+, ↑VNaOH , ↑[H+] INCREASE, ↓pH
case 7/2) The ratio provided by the formula above corresponds to the concentration Conceptual: More NaOH titrant was added so it will appear that there are more H+ in the flask when
of H+ in the titrated solution (E. flask) and not on the sample (packaging itself) in fact you just uncontrollably added an excess of the titrant.
- The diluted concentration of the titrated solution need to be increased or related to 3.) Last rinsing of the burette is water and not NaOH titrant. Standardization. Effect on
the actual sample. This is done by multiplying it to the dilution factor. VNaOH.
Conceptual: If thereis water lining the inner walls of the burette, then the introduced titrant that will
be immediately used for the titration will be diluted. DECREASE in [NaOH] more (INCREASE in VNaOH)
For H2CO3: H2CO3 + 2NaOH  2H2O + CO32- is needed to neutralize the specified mass of KHP.
𝑚𝑚𝑜𝑙 𝑁𝑎𝑂𝐻 𝑚𝑚𝑜𝑙 𝐻2 𝐶𝑂3
Formula: This is evident on the formula, decreasing [NaOH] would’ve resulted to an increase of the
𝑚𝑚𝑜𝑙 𝐻2 𝐶𝑂3 (𝑉𝑓−𝑉𝑜)𝑚𝐿 𝑁𝑎𝑂𝐻 𝑡𝑖𝑡𝑟𝑎𝑛𝑡 ( )( ) 70𝑚𝐿 𝑝𝑟𝑒𝑠𝑒𝑛𝑡 𝑣𝑜𝑙𝑢𝑚𝑒
[H2CO3] = = 𝑚𝐿 𝑁𝑎𝑂𝐻 𝑡𝑖𝑡𝑟𝑎𝑛𝑡 2 𝑚𝑚𝑜𝑙 𝑁𝑎𝑂𝐻
𝑥 volume of it needed.
𝑚𝐿 𝐻2 𝐶𝑂3 𝑚𝐿 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 (𝑖𝑛 𝑡ℎ𝑒 𝑒𝑥𝑝𝑡 50+20 𝑚𝐿) 20 𝑚𝐿 𝑎𝑐𝑡𝑢𝑎𝑙 𝑠𝑎𝑚𝑝𝑙𝑒 4.) Bubbles on the Burette Tip not removed. Standardization. Effect on [NaOH]
Formula: A larger volume difference for the titrant will be recorded since parts of it is just air. ↑VNaOH
For CH3COOH: CH3COOH + NaOH  H2O + CH3COO- , ↓[NaOH] DECREASE
Conceptual: More of the Titrant needs to be added since part of it is air. It seems it is weaker to
𝑚𝑚𝑜𝑙 𝑁𝑎𝑂𝐻 𝑚𝑚𝑜𝑙 𝐶𝐻3𝐶𝑂𝑂𝐻
(𝑉𝑓−𝑉𝑜)𝑚𝐿 𝑁𝑎𝑂𝐻 𝑡𝑖𝑡𝑟𝑎𝑛𝑡 ( )( 𝑚𝑚𝑜𝑙 𝑁𝑎𝑂𝐻 ) neutralize a given amount of KHP standard.
[CH3COOH] = 𝑚𝑚𝑜𝑙 𝐶𝐻3𝐶𝑂𝑂𝐻
= 𝑚𝐿 𝑁𝑎𝑂𝐻 𝑡𝑖𝑡𝑟𝑎𝑛𝑡
𝑥
51 𝑚𝐿 𝑝𝑟𝑒𝑠𝑒𝑛𝑡 𝑣𝑜𝑙𝑢𝑚𝑒
𝑚𝐿 𝐶𝐻3𝐶𝑂𝑂𝐻 𝑚𝐿 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 (𝑖𝑛 𝑡ℎ𝑒 𝑒𝑥𝑝𝑡 50+1 𝑚𝐿) 1 𝑚𝐿 𝑎𝑐𝑡𝑢𝑎𝑙 𝑠𝑎𝑚𝑝𝑙𝑒 5.) Bubbles on the Burette Tip not removed. Unknown Analysis. Effect on [H+]
Formula: More of NaOH titrant needs to be added, it is partly air in the burette.
↑VNaOH , ↑[H+] INCREASE, ↓pH
Conceptual: More of the titrant is added, unaware that it is partly air. One might assume that there
are more H+ in the flask because more OH- was needed to neutralize it.

CHEM 16: GENERAL CHEMISTRY I LABORATORY EXPERIMENT 4 POST LAB DISCUSSION MOLINO, R. J. E.
 6.) Droplets of titrant remained in the mouth of the flask, even if endpoint has already
been achieved. Unknown Analysis. Effect on H+.
Formula: More NaOH was added than should be to reach the endpoint. ↑VNaOH , ↑[H+] INCREASE,
↓pH
Conceptual: More titrant was added than necessary. It seems there are more H + in the sample when
in fact none of those extra drops went down to neutralize the solution.
7.) Excess NaOH is present in the burette containing the KHP standard. Standardization.
Effect on [NaOH]
Formula: If trace NaOH is already present in the flask even before the titration then parts of the
weighed KHP will be neutralized already. Fewer KHP will react with the acid on the burette. Fewer
titrant is needed. ↓VNaOH, ↑[NaOH]
Concept: It seems the titrant is more concentrated/ potent since less of it is needed, when in fact its
concentration is not as strong, it just reacts with less of the primary standard.
8.) 1mL pipette used to get vinegar sample is still wet. Unknown Analysis. Effect VNaOH
titrant.
Formula and Concept: If the pipette used to get the sample is wet, then it will be diluted, less of the
titrant is needed to neutralize it ↓[CH3COOH], ↓VNaOH, when in fact the sample solution has more H+
(requires more titrant)
9.) Sample to be titrated is exposed in air and not covered prior to titration.
Carbon Dioxide in Air might collide with water on the surface to produce carbonic acid.
CO2(g) + 2 H2O(l)  H2CO3(aq)
VNaOH increases since more H+ needs to be titrated. Increase in [H+]

This reaction is also the reason why the pink endpoint seems to faint after a while. The solution
reverts to acidic after CO2 reaction to form the H+ releasing H2CO3.

CHEM 16: GENERAL CHEMISTRY I LABORATORY EXPERIMENT 4 POST LAB DISCUSSION MOLINO, R. J. E.