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In the practical course in Analytical Chemistry during my first semester at university, I had to titrate a lot. Thinking back on it, I remember carefully dosing titrant with the glass buret, the cumbersome process of refilling the buret, and the constant suspicion that I hadn’t correctly chosen the endpoint.

Everyone in class kept getting different results—but we were never quite sure why. At the time, I wasn’t as experienced as I am now. Today, after 10 years of experience in titration, I’ve learned that the results of manual titration depend quite a lot on the person carrying it out. Here are the top error sources in manual titration and how you can avoid them.  

Choosing the right indicator I’m sure you’ve learned at some point that the pH value of the titration endpoint depends on the acid dissociation constant (Ka) of the acid and base that are used. If a strong base is titrated by a strong acid, the pH value at the endpoint is around 7. The titration of a strong base with a weak acid shifts the endpoint towards the alkaline range. The titration of a strong acid with a weak base will result in an endpoint in the acidic range. This explains why several different indicators are used in acid-base titrations. But which is the right one to choose?
The chart above shows some of the most frequently used pH indicators. You can probably imagine that you won’t get correct results when the pH of your endpoint is around 7, but you use crystal violet or methyl orange as the indicator. Luckily, most standards and SOPs specify an indicator. Follow the instructions, and you’re on the safe side!

Endpoint recognition is subjective

The problems really start when you try to recognize the endpoint. Have you ever thought about the nuances of the color change?

Above, you see five stages of an acid-base titration of c(HCl) = 1 mol/L with c(NaOH) = 1 mol/L. The only difference between each image and its predecessor is one additional drop of titrant. Where would you choose the endpoint in this case?

Is the endpoint reached in picture 1, where only a faint pink is visible? Or is it reached in picture 3 where the color becomes more intense? Or even in picture 5, at which point the pink color is most vibrant? Between picture 1 and picture 5, just four drops of titrant were added. With the pharmaceutical definition of a drop as a volume of 50 µL, this corresponds to 200 µL of titrant or about 7.3 mg of hydrochloric acid—an enormous error.

Reading the buret volume

Do you remember how to correctly read the buret? You have to stand on a footstool and make sure that you read the meniscus value horizontally. Do you know why?

The volume reading depends upon the angle from which you view the buret. In the case shown here, the readings vary up to 0.2 mL (200 µL) from the actual value, depending on the reading angle. The more your line of sight deviates from the horizontal, the more inaccurate the reading—and the result. You can assume an average error of 200 µL. This is a lot for a titration, as I showed in the previous example!

Improving objectivity and accuracy

How can you eliminate these errors? The easiest one to overcome is the reading error. The solution for this is to use an electronic buret. When using an electronic buret, all you need to do is fill it with the titrant and then you press a button. The device automatically measures the volume and gives you a digital readout. Using an electronic buret ensures already a high level of objectivity for your results.

It also improves the accuracy of your results. I don’t have to tell you how important accuracy is in analytical chemistry, but I’ll give an example. Imagine you determined the purity of gold at 90%, but in reality, it’s 99% pure. You would lose a lot of money when selling your gold under this pretense!

Earlier, I showed that visual endpoint recognition using a color indicator can result in errors of up to 200 µL. An inaccurate buret reading can lead to an additional 200 µL error. While using an electronic buret doesn’t help you achieve a more objective endpoint recognition, it does reduce the minimum volume addition per drop: it’s no longer 50 µL, but can be as small as 0.25 µL depending on the cylinder volume you use. This substantially lowers the error resulting from endpoint recognition. The following minimum volume additions are common:

The next step: Automated titration

If you want to overcome all sources of error described in this post, you’ll have to switch to automated titration, or autotitration. In this case, you will use a sensor to measure pH change in the sample and a mathematical algorithm to detect the endpoint—an indicator isn’t required anymore. Additionally you have the same precision as with the electronic buret.

Want to learn more?

Download our free White Paper:

Manual vs. Automated Titration: Benefits and Advantages to Switching

Post written by Iris Kalkman, Product Specialist Titration at Metrohm International Headquarters, Herisau, Switzerland.

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