ANALYTICAL CHEMISTRY DR. MOHAMMAD KHANFAR EIGHTH LECTURE ACID BASE TITRATION SHAMS W. ALSHIKHLY SUNDAY 6TH OF JULY ,2014 In the last lecture we talked about back titration and figured out that the method is used for: Parts of Titration Volatile substances Analyte: strong acid/base, weak acid/base. Titrant: always strong acid or base. Insoluble substances Indicator: The same type of analyte (acid or base) but Rapid reaction when excess is added Substances which require heating What is the principle of back titration? Addition of excess of standard solution (titrant) to a weighed amount (or volume) of sample, and determination of excess (un-reacted) titrant using secondary titrant. E.g. Silver with Phosphate. weaker, the most important properties of the indicator are: 1) pKa value should be lower than the analyte when it is base, and higher when it is acid. 2) pKa value should fall within inflection region1. Let’s assume that we have an inflection point between (4-8 pH), the best indicator would be the one that has pKa = 6 or ± 1 Titration Curves Analyte = Acid Titrant = Base Now we will start with: Acid/Base Titration (neutralization titration) In acid/base titration, the analyte is either strong acid, strong base or weak acid, weak base. Titrant is always strong acid or base. Indicator is always weak acid or weak base depending on the analyte and it’s always weaker than the analyte. Strong acids HCl H2SO4 HClO4 Strong Bases NaOH KOH CH3ONa R-O-Na+ Infliction region: the point when the analyte is completed with one drop excess of the titrant giving me sharp difference in pH. 1 1 ANALYTICAL CHEMISTRY DR. MOHAMMAD KHANFAR EIGHTH LECTURE Analyte = Base Titrant = Acid ACID BASE TITRATION SHAMS W. ALSHIKHLY SUNDAY 6TH OF JULY ,2014 The stronger the base or acid the sharper the inflection AFTER the equivalence point So, it would be easier to detect the endpoint. ⬆Sharpness ⬆Accuracy in end point. Analyte = HCl or Ch3COOH Titrant = NaOH What is the effect of strength in the acidity or basicity on the titration curve? Analyte = HCl Titrant = NaOH or CH3ONa Post equivalence point of CH3COOH is little bit higher than HCl because the product of CH3COOH is conjugate base but the product of HCl will be neutral compound neither acidic nor basic. 2 ANALYTICAL CHEMISTRY DR. MOHAMMAD KHANFAR EIGHTH LECTURE Indicators Phenolphthalein: ACID BASE TITRATION SHAMS W. ALSHIKHLY SUNDAY 6TH OF JULY ,2014 base, so I will have a basic indicator , when I start titration , the basic indicator should have a pKa HIGHER than the analyte . One of the most used indicators is Phenolphthalein, Look at its curve below: Methyl Orange: pKa = 9.4 Phenolphthalein is colorless by itself, but when it loses a proton, it turns into pink; which means that it is acidic, a very weak acid; because of its high pKa. When using phenolphthalein we have to be sure that the inflection point of the titration curve will have pKa=9.4 in the middle of its pH values or ± 1 Its red in the acidic form (pKa = 3.7), and yellow in the basic form (pKa 10.3). Phenolphthalein is used as indicator, it is used as acid in acidic analytes, can I use it as base? It can be used in acidic analytes and basic analytes, at the first place it is an acid but when added into a basic solution its will turn into basic indicator. Its conjugate base has pKa = 4.6, so, yes! I can use the conjugate base when the analyte is basic. We have to be sure that the pKa will fall within the inflection point before choosing it as indicator. Did you understand? Ok, let me clarify 3 At the first place we use phenolphthalein as acidic indicator, but it is very weak acid, when we put it in a basic analyte, it will turn rapidly into a conjugate ANALYTICAL CHEMISTRY DR. MOHAMMAD KHANFAR EIGHTH LECTURE ACID BASE TITRATION SHAMS W. ALSHIKHLY SUNDAY 6TH OF JULY ,2014 For soft and colored copy go to www.ispatula.net Before any base is added, how much is the pH (at zero time)? Other indicators: pH = − log[𝐻𝐶𝑙] pH = − log 0.05 = 1.3 After addition of 10 ml (before equivalence point) of NaOH, how much is the pH? Look at the above table, pKa should always fall within the pH range. Calculations How can we calculate pH on any point within the titration curve? I added 10 ml NaOH which is consumed by HCl completely, so my solution here is the excess of HCl. Now I have to determine how many moles of HCl are remained after the addition of NaOH, we said that to reach the equivalence point we need 25 ml of NaOH, which means all of the HCl is consumed and I have excess of NaOH, but in 10 ml I have the opposite condition. Total moles of HCl = 0.05 M X 0.05 L = 0.0025 mole Total moles of NaOH = 0.1 M X 0.01 L = 0.001 mole Number of moles after the addition of 10 ml NaOH = 0.0025 – 0.001 = 0.0015 mole HCl Example 1: pH = − log[𝐻𝐶𝑙] Titration of NaOH 0.1 M with HCl 0.05 M, 50 ml. Analyte is HCl, NaOH is the titrant pH = − log [ 0.0015 0.05 ] = 4.1 How much is pH on the equivalence point? 7, always 7 when the titrant and the analyte are STRONG How much NaOH I need to reach the equivalence point? M1V1=M2V2 see the footnote 2 Our greatest weakness lies in giving up. The most certain way to succeed is always to try just one more time. Thomas A. Edison 50 X 0.05 = 0.1 X VNaOH = 25 ml NaOH Only when the reaction ratio is 1:1,e.g. H2SO4 is not 1:1 so it can’t be used directly 4 2
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