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Why Acid?

This technical article explains why formic acid is use as additive in many LC-MS methods.
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Written byJohn Dolan
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This technical article addresses why formic acid would be specified as an additive for the mobile phase in an HPLC method. Formic or trifluoroacetic acid at 0.1% concentrations are common, especially for LC-MS work. There are a number of reasons for adding an acid at low concentration to the mobile phase. Let’s look at two of these: the influence on the column and the sample.

Silica acts as the support material for most reversed-phase columns. As we saw in earlier articles ('Silica Purity - Metals' and 'Silica Purity - Silanols'), the silica surface can vary depending on its source and how it is treated. However, we can consider the silica surface as somewhat acidic, with pKa values in the 4.8 region often cited for low-purity, type-A silicas, and higher pKa values for the high-purity, type-B silicas in more common use today. Ionized silanol groups interact through ion-exchange with ionized bases, and are a major factor in peak tailing for basic solutes. One way to minimize this problem is to suppress the ionization of the silanol groups. Thus, when the mobile phase pH is <≈3, the silica surface silanols are mostly suppressed, so cation-exchange interactions are minimal.

By reading the full article, you will learn how 0.1% formic acid is the favoured go-to additive in many LC-MS methods and the reasons why this should be the case.

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Meet the Author(s):

  • John Dolan

    John Dolan is considered to be one of the world’s top experts in HPLC. He has written more than 300 user-oriented articles on HPLC troubleshooting over the last 30 years, in addition to more than 100 peer-reviewed technical articles on HPLC and related techniques. His three books (co-authored with Lloyd Snyder), Troubleshooting HPLC Systems, Introduction to Modern Liquid Chromatography (3rd edn), and High-Performance Gradient Elution, are standard references on thousands of desks around the world. He has taught HPLC training classes around the world to more than 10,000 students.

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