Revision as of 01:19, 25 July 2009

This is the first of three articles intends to be an overview over pH, the importance in brewing, how it affects various brewing processes, how it can be measured and controlled. It tries to keeps math to a minimum in order to make the subject understandable for everyone.

What is pH ?

pH is a measure of the acidity of a solution. It is a measure of the concentration of hydrogen ions (H⁺; proton). The higher the concentration of hydrogen ions in a solution the more acidc it is and the lower their concentration the more basic it is. In pure water (H₂O) not all of the hydrogen (H) and oxygen (O) ions are bound in water molecules. A small number of these molecules are broken up (disassociated) into protons (H^-) and hydroxide (OH^- ions (see figure 1). The ion H⁺ concentration of freshly distilled water, which is water that didn't have a chance to pick up any minerals or gases corresponds to a pH of 7 which is the neutral pH. A acidic solution will have a pH below 7 and a basic solution has a pH greater than 7. Once distilled water stands in air it will pick up CO₂ and the pH falls to about 6.5.

(Technically free protons (H+) don't exist in water. They react with water molecules to form a hydronium ion (H₃O⁺ but for the sake of simplicity in this article I will refer to them as protons as all that matters is their concentration and their electrical charge)

The pH scale is not a linear measure of the proton concentration but a logarithmic one. This means that a change of 1 pH unit doesn't change the proton concentration by 1/7 of that of distilled water. Instead a solution with a pH of 6 has a 10 times higher proton concentration compared to distilled water. And a pH of 5 means it has a 100 times higher proton concentration. Likewise a solution with a pH of 8 has only 1/10 the proton concentration of distilled water. For each pH unit up the concentration is divided by 10 and for each pH unit down it is multiplied by 10.

weak acids and bases

Figure 2 - The relationship between the percentage of an acid (acetic acid (vinegar), C₂H₄O₂) and its conjugate base (acetate, C₂H₃O₂^-). The pH at which the concentration of acid and its conjugate base are equal is called pKa and depends on the type of acid and the temperature. For acetic acid at 20C (68F) it is 4.75. Below that pH an increasing amount of acetate anions will absorb protons and become acetic acid. Above that pH an increasing amount of acetic acid will loose protons and become acetate anions. Or to express it another way, in order to decrease the pH protons have to be added to convert acetate anions into acetic acid

When we later discuss the effects of pH we will come across one common theme: the disassociation of H+ and OH- ions from larger molecules. A substance that donates H+ to or accepts OH- ions from its environment is called an acid. It lowers the pH. A substance that accepts H+ or donates OH- is called a base and it raises the pH. When acids and bases are brought together they neutralize each other by forming a salt and water.

When strong acids or bases are dissolved in water they readily dissolve and each molecule donates H+ or OH-. Depending on the concentration of the acid or base the result is a dramatic pH drop towards 0 or a pH rise towards 14. But most acids and bases we will deal with in brewing, especially when we talk about the effects of pH, are weak acids. A weak acid is an acid where only a portion of its molecules disassociate in water. The exact ratio depends on the pH of the solution, temperature and the type of acid. The same is true for weak bases.

When an acid disassociates it leaves behind a negatively charged remainder, called conjugate base. Since the proportion of disassociated weak acid molecules depends on the pH, pH controls how many negatively charged conjugate bases are present. In case of weak bases the remainder (called conjugate acid) that is left after the disassociation of a hydroxyl ion (OH-) or the acceptance of a proton is positively charged. pH controls their concentration as well. Figure 2 illustrates the relationship between the ratio of acid and conjugate bases on the example of acetic acid (vinegar).

Later we will see how the weak acids like tannins and complex molecules build from many different weak acids and weak bases (proteins for example) are affected by the pH of their environment though the pH dependent disassociation of H+ and OH-.

pH buffers

One more basic chemistry phenomenon needs to be discussed before we can jump into how pH can be measured: buffering capacity and pH buffers

pH only tells us about the balance between protons (H+) and hydroxyl (OH-) in a solution. It doesn't tell us how strongly it is held in place. I.e. it may take the addition of only little amounts of an acid or a base to change the pH or it may take a lot to change it. What is keeping the pH in place are weak acids, bases and their salts. They all act act as pH buffers.

Figure 3 -

We saw in the last section that the ratio between conjugate base and acid molecules and their respective acid and base molecules depends on the pH and the type of acid/base itself. Lets look at a solution of lactic acid. At a pH of 3.86 half of the molecules are still undisassociated (lactic acid) and the other half is disassociated (H+ and lactate). When we now try to lower the pH by adding more H+ to the solution through the addition of a strong(er) acid the ratio of disassociated to undisassociated lactic acid molecules shifts towards less disassocuated ones. This means that some of the H+ that was added will be consumed by creating more lactic acid molecules from the existing lactate molecules. This in turn reduces the number of H+ that are available to lower the pH and the pH doesn't fall as much as it would have if the lactic acid was not present or present at a lower concentration. The lactic acid acted as a buffer. The amount of stronger acid that needs to be added to lower the pH depends not olny on the desired pH difference but also on the concentration of lactic acid.

This also works in the other direction when a strong base is added. In this case the rise in pH shift that more lactic acid molecules disassociate and free protons (H+) which need to be consumed by the hydroxyl ions (OH-) released by the base before the pH can rise.

In mashing and in beer there is not a single acid or base that acts as a buffer but a wide variety which have different pH at which they 50% disassociated and 50% undisassociated. But later when we talk about water we will come back to the major buffering agent which are the various forms of carbonates: carbonic acid, bicarbonate and carbonate. It's concentration will tell how much acid it takes to move the water pH into a favorable pH for mashing.

Buffer solutions also provide a stable pH reference for the calibration of pH meters. These solutions have been mixed precisely from acids/bases and salts to hold their pH steady even in the presence of small contaminations with other acids or bases.

Measuring pH

Now that we looked at how pH affects various brewing processes you might be interested in measuring pH. And that problem can be almost as complex as the effect of pH. For the home brewer 3 viable methods of testing pH exists: lithmus paper, colorpHast strips and pH meters. In general the cheaper the means of pH testing the less accurate the result is.

Lithmus paper and economy pH strips

These are the strips that you know from science class in school their function is based on the change of color of a pH indicator (in this case an extract from lichens) that is impregnated into paper strips. Below a pH of about 4.5 its color is red and above pH 8.5 its color is blue. At pH values between it will have different shades of colors. The pH is determined by matching the shade of color to a color scale that is supplied with the strips.

The pH indicator acts as a weak base or acids. That means that it accepts or donates protons (H⁺) based on the pH of the surrounding solution. As seen in the ìweak acids and basesî section in the beginning the ratio between the acid (when it still has all of its protons) and its base (when it donated or accepted a proton) depends on the pH and will change with the pH. What makes these indicators so unique is that these two forms of the indicator have a different color. For example if the indicator acts like an acid then at low pH un-disassociated form is dominant because there are already enough protons in the solution and it doesn't need more. This means that the indicator will take the color of the un-disassociated form. Ar a higher pH the disassociated form will be dominant because it looses its protons to an environment that is low in protons. When a pH is considered low or high in protons depends on the nature of the indicator and different indicators will show color changes at different pH ranges. In the case of litmus paper it is a range of indicators that change color at various pH ranges throughout the papers pH range.

Since the indicators itself act as acids or bases they actually change the pH of the tested solution. This is not a problem in sufficiently buffered solutions. And we discussed the concept of pH buffers in the beginning. It is important to think about the buffering capacity of the solution that is tested for pH with any of the means of testing pH. The less its buffering capacity the less accurate the pH measurement will be. Luckily most solutions that we test for pH in brewing are strongly buffered and we don't have to worry about this effect. The only one that is not strongly buffered is very soft or even distilled water. Here you can easily get false readings but the pH of the brewing water is of little importance anyway, especially when buffered only weakly, as we will see later.

A good analogy to to testing the pH of strongly and weakly buffered solutions is measuring the temperature of a small or large sample. If the sample is small the temperature of the probe will change its temperature because as the sample and the probe reach a temperature equilibrium the temperature of the sample has to change. This obviously doesn't matter anymore once the sample size is much larger than the temperature probe. The same applies to testing pH and the buffering capacity of the sample.

colorpHast strips

EMD chemicals makes a range of pH test strips that are a significant improvement over litmus paper or other economic pH test strips. The product is called colorpHast and has these advantages:

• the indicator will not run and leach out of the test strip
• the testing range is narrow enough to read the strips with +/- 0.2 pH point precision
• the strips are easily matched against the color scale
• they are designed to be used in samples that contain proteins and don't exhibit a protein error [6]

Another important advantage is that they don't require calibration like a pH meter does. But their precision is limited to ~+/- 0.2 pH unit which is sufficient for testing the mash pH but some brewers like to have greater precision in their pH measurements. In comparative tests between the colorpHast strips and a pH meter I noticed a constant error of about 0.3 pH units. I.e. for most of their pH range the strips read about 0.3 pH units lower than the pH that was determined with a pH meter (More info can be found here colorpHastStrips vs. a pH meter and here micro mashing experiments

pH meters

A completely different approach for taking pH readings are electronic pH meters. The heart of these meters is a glass electrode which converts the H+ concentration into a voltage that can be measured with a volt meter. Since this voltage is proportional to the logarithms of the H+ concentration it is also proportional to the pH in other words the pH of the sample is a linear function of the voltage that is measured at the probe. Every liner function is determined by 2 parameters: offset and slope. The slope can be calculated and is about 60 mV per pH unit [7]. This slope may change as the probe ages.

A single point calibration uses a single solution of known pH. This solution is called a calibration buffer and common buffer pH are 4.00, 7.00 and 10.00. Since such a single point calibration can only determine the current offset of the probe a better calibration procedure uses 2 buffers. Since most brewing related samples have a pH below 7 calibrating the pH meter with a 4.00 and a 7.00 buffer is recommended. This calibration should be carried out regularly. Especially when the probe has not been used for a while.

When the pH of a sample is measured it is also important to known what the temperature of the sample is. This is important for 2 reasons. The temperature of the sample affects its H+ concentration and therefore its pH. This is the result of changing H+ and HO- disassociation balances in the sample and is substrate specific. In some cases the pH rises with the temperature or falls as the temperature rises or even follows a curve. For wort it has been reported that the pH at mash temperatures (65C/150F) is about 0.35 pH units lower than at room temp and at mash out temperatures (75C/170F) it is even 0.45 pH units lower [8]. The temperature dependent change of pH is also important for the calibration of the pH meter since the buffer solutions only have their nominal pH at a specific temperature. This temperature is usually room temperature (25C/77F) and many buffer manufacturers also supply tables with their buffers that show how their pH changes with temperature. I have made it a habit to always calibrate my pH meter with buffer solutions at room temperature (25C +/- 1).

In addition to the pH of the sample the temperature also affects the response of the pH electrode. This effect is specific to the electrode and will not change from sample to sample that's why many pH meters are equipped with automatic temperature correction (ATC) where a separate temperature sensor, which is oftentimes integrated into the probe, is used to measure the temperature of the sample and and taken to correct for the temperature error of the pH electrode. This means that the pH measured with an ATC pH meter still changes based on temperature but that change is only the result of temperature dependent H+ concentration in the sample.

If the pH is also dependent on temperature what temperature should a sample be measured at? The answer is that any temperature works as long as it is noted with the pH measurement. But to make comparing of pH measurements easier it is best to take them at the standard room temperature of 25C or 77F. Some brewers use their pH meter to test the pH directly in the mash but testing hot liquids reduces the lifetime of the probe which I don't recommend this practice. We will come back to this topic when we look at the target pH for mashing and boiling.

The increased precision of a pH meter comes at a price. Not only are they more expensive, the probes need replacement after 1-2 years. Good care can extend the life of the probe. Here are some tips when working with pH meters:

- always store in a pH meter storage solution and never in water even it it is distilled water. A pH meter storage solution contains salts that help the pH meter recover. - never let the probe dry out - thoroughly rinse the probe with distilled or deionized water, after removing from the storage solution, between measuring samples or calibration buffer and before returning to the storage solution. I flick with the wrist also removes the excess water from the probe. - measur cooled samples only - don't scratch or rub the glass bulb. It is coated with a sensitive layer that is integral to its function and it is rather fragile