Peter Barham’s presentation at the MG seminar in Copenhagen focused on how food can be used to make students interested in physics and chemistry (not a bad thing, especially since 2011 is the International Year of Chemistry) -Most people think science is boring and difficult, he said. But demos can help bring science to life, and believe it or not – experiments are much better when they go wrong. Using balloons, champagne, potatoes and liquid nitrogen Peter Barham proved his point. As an example he asked the audience how much air weighs. He first filled a balloon with a few milliliters of water, then squeezed out all the air, tied a knot and heated the water in the microwave until all had evaporated. The first balloon exploded since he used to much water (this shows that water expands when boiled and that balloons are not infinitely stretchable!). Using a little less water for the second balloon, everything worked fine. Assuming that steam has approximately the same density as air, the size of the balloon can be measured and from this the weight of air be calculated. One finds that the volume of the water increases by a factor of approximately 800x.

There will be more foam when champagne is poured into a dirty glass due to more nucleation sites providing the dissolved carbon dioxide with more escape routes.

Ever heard about how a spoon in the neck of an opened champagne bottle can keep the champagne fizzy? Well unfortunately this is a kitchen myth. The only thing that helps is keeping the bottle cold. The spoon has no effect whatsoever. And the balloon once cooled can help illustrate this. When all the steam had condensed there was a significant amount of gas left in the balloon (remember that all the air was squeezed out to start with). This illustrates that gases are soluble in water at low temperature, but not at higher temperature. When water is boiled the gas escapes. Gas (and in particular carbon dioxide) is more soluble at lower temperatures, and that is the explanation why champagne may retain quite a lot of the fizz if stored cold. The spoon is only there to confuse you!

How long does it take to boil a potato?

Next question was: How long does it take to boil potatoes? Since the visual appearance of a potato changes around 60 °C it is possible to monitor heat transfer by simply slicing a potato in two. If boiled in water a nice ring with a slightly darker color indicates how the heat travels uniformely towards the center. If you plot the width of the ring against the square root of the time you get a nice straigth line. However, if heated in a microwave a different pattern emerges. The wavelength of microwaves is on the order of several centimeters and as a consequence the distance between hot and cold areas are about 2 cm. Slicing a microwaved potato shows how only one side has been heated. This is the simple reason why food heated in a microwave oven must be left to stand for a while to allow the heat to diffuse.

When heated in boiling water the heat travels uniformly towards the center of the potato as evidenced by the “ring” that occurs once the temperature reaches 60 °C.

When heated in a microwave there will be hot and cold areas as illustrated with this potato.

Peter Barham also mentioned the experiment that demonstrates the difference between taste and aroma. If you close your eyes, hold your nose and have a friend give you either a piece of apple or pear, you’ll have a difficult task saying which is which. But the second you let go of your nose you recognize what you have in your mouth. The experiment can also be conducted with lemon and lime or other fruit pairs with similar textures. The reason for this is that when you hold your nose, hardly any air from the mouth will enter your nose through the retronasal passage. As a result you will not be able to “smell” what’s in your mouth. But the second you let go of your nose, air can pass freely and you immediately smell what’s in your mouth. This is also the reason why the aroma of food is subdued if you have a cold and a runny nose.

Close your eyes, hold your nose and experience the difference between taste and smell! Apples and pears taste remarkably similar when the aroma is blocked out by holding your nose.

Peter’s last demonstration was liquid nitrogen ice cream and an attempt to break the current world record of 10.34 seconds. More on that in the next post

Cheeseburger in hydrochloric acid

Do ice cubes made with heavy water float or sink?

Exotic ways to cut through butter

Spectacular ways of destroying pumpkins for Halloween

Tea chemistry

See Martyn Poliakoff boil an egg

(Martyn mentions that the yellow color of egg yolks is due to a sulfur containing compound, but I’m not really convinced he’s right about that. The yellow color is mainly due to a group of chemical compounds called xanthophylls which have long conjugated double bond systems that absorb light. And BTW – if you want to dissolve the egg shell in your own kitchen: skip the hydrochloric acid and use vinegar instead.)

Baking a cake in the lab with akward equipment…

… and then figuring out what to do with the cake
(it wasn’t eaten since it was made in a chemical lab)

Mirror images: Carraway and spearmint

Fun chemistry with Crispy creme eggs

Chocolate and roses for Valentines day

As the name suggests, the TGIF posts are a little less serious than what I otherwise post here at Khymos. I hope you enjoy it

Many cookbooks suggest the following for boiling eggs: 3-6 min for a soft yolk, 6-8 min for a medium soft yolk and 8-10 min for a hard yolk. If you are satisfied with this, there is no need for you to continue reading. But if you’ve ever wondered whether the size of an egg has any impact on the cooking time you should read on. And if you search the ultimate soft boiled egg we share a common goal! From a scientific view point, a cooking time of approximately 3-8 minutes to obtain a soft yolk is not very precise. A number of important parameters remain unanswered: What size are the eggs? Are they taken from the fridge or are they room tempered? Are they put into cold or boiling water? And if using cold water – when should the timer be started? When the heat is turned on or when the water boils? And would the size of the pan, the amount of water and the power of the stove top matter?

A formula for boiling eggs?

I still remember the very first time I heard about a formula to calculate the cooking time for eggs. I was in high school and as a recipe for the ultimate nerd the egg formula gave me a good laugh. Now – many years later – I count myself to this group of nerds And thanks to the internet, google and Peter Barham’s book “The Science of Cooking” – I have been able to find out much more. I haven’t been able to track down the formula I heard mentioned, but the best documented formula nowadays is derived by Dr. Charles D. H. Williams, a lecturer in physics at University of Exeter. He has set up a nice page on the science of boiling eggs and there’s even a pdf with the full derivation of the formula. Given the starting temperature of the egg T_egg, the temperature of the water T_water and the desired temperature T_yolk (all in °C) at the yolk-white boundary, the cooking time t (in minutes) of an egg with mass M (in grams) is given by:

Whenever possible one should use weight measurements in the kitchen, but some times an accurate balance is not available and in those cases we can turn to the Peter Barham’s formula which is published in “The science of cooking”. The circumference of an egg is easily measured around the thick end using a piece of string and a ruler. I used to have a piece of string with three knots at 13, 14 and 15 cm respectively to make it even simpler. The cooking time t (in minutes) for an egg with a circumference c (in centimeters) is given by:

Former colleagues of mine at the University of Oslo have made a nice flash animation to do calculations with Barham’s formula if you’re not too keen to dig out your calculator. Barham states that his formula gives the time for the centre of the yolk to reach the temperature T_yolk whereas Williams mention in the derivation of the formula that it calculates the time for the yolk-white boundary to reach T_yolk. I’m not able to tell whether the formulas actually differ in this respect or not (comments are welcome on this issue!). A comparison of the two formulas for a set of 50 eggs which I weighed and measured shows that for T_yolk = 63 °C and T_water = 100 °C they are quite similar, except for the larger spread of the circumference measurements (see plot below). For higher T_yolk or lower T_water Williams’ formula consistently gives longer cooking times than Barham’s formula. It remains to be seen which of the formulas will be closer to the truth.

The graph shows the cooking time for 50 eggs (sorted by increasing mass) calculated from the mass and circumference using the two formulas shown above with T_yolk = 63 °C, T_water = 100 °C and T_egg = 4 °C. For the given conditions the two formulas give similar results. The most striking lesson learnt is that measuring the circumference is in fact not very accurate, hence the larger spread of these points.

The doneness of the egg depends on the temperature of the white and the yolk. Egg white starts to coagulate in the range 62-65 °C. At these temperatures it is the most heat sensitive protein, the ovotransferrin, which constitutes 12% of the egg white, which coagulates. The major protein of egg white, ovalbumin, makes up 54% of the white and doesn’t coagulate until the temperature reaches 80 °C. The yolk begins to thicken around 65 °C and sets around 70 °C. Further heating to around 80-90 °C produces the crumbly texture typical of hard boiled eggs. Many of these changes are nicely illustrated in the picture of sous vide cooked eggs below, but the changes are also summed up in the following table:

At sea level, the temperature of boiling water is 100 °C. At higher altitudes, the boiling is lowered. As a rule of thumb, the boiling temperature of water is lowered 0.3 °C for each additional 100 m above sea level. For an accurate calculation, check out his calculator. As we shall see later, the formula can of course also be used prepare eggs at sea level, using water kept at temperatures less than 100 °C. Lastly we must know the starting temperature of the egg which will typically be 4 or 20 °C.

Based on T_water = 100 °C, T_egg = 4 °C and T_yolk = 63-67 °C I’ve prepared plots for the range of 50 eggs used in the previous graph. If the circumference or mass of an egg is known, the boiling time in minutes can easily be determined from the graphs. I’ve also prepared downloadable pdfs with the circumference and mass plots.

Cooking time for eggs with given circumference or mass to reach to reach 63, 65 and 67 °C respectively at the yolk-white boundary with T_water = 100 °C and T_egg = 4 °C (click for larger image or download pdfs with circumference and mass plots)

But is this the perfect egg?

No actually not… keep reading! The problem with using boiling water is that while you do heat the yolk to the desired temperature, you have virtually no control with the temperature of the white. If your water holds 95-100 °C, so will the white (or at least the outer most part of the white). This gives it a firm, rubbery texture. So the problem is, to put it differently, that we want to heat the yolk to somewhere above 65 °C, but we do not want to heat the white above 80 °C. The solution to this problem is to “boil” the egg at a temperature lower than 100 °C, which means not to boil it at all but rather sous vide it! Eggs are perfect for sous vide because you can just drop them into the water bath as they are. No plastic bags or vacuum packaging are required. Douglas Baldwin has cooked eggs sous vide for 75 min at different temperatures ranging from 57.8 to 66.7 °C as shown below. Notice how the egg whites and egg yolks change at the different temperatures.

Composite image of eggs cooked sous vide for 75 min at the indicated temperatures (Photo: Douglas Baldwin. Picture used with permission.)

The surprising thing with some of the sous vide eggs is that they are inverted (or opposite boiled). The white is still runny while the yolk is set. If you would like to try this but don’t have a thermostated water bath for sous vide you can improvise a little. The thermostat most people do have in their kitchen is the baking oven (at least those with electric stoves). Preheat your oven to 70 °C. Then heat 1 L of water to 65-70 °C, put the eggs in, cover with a lid and leave the pan in the oven for one hour. The tricky thing here is that oven thermometers are notoriously wrong so use a separate handheld thermometer to check your oven. With some trial and error you should be able to obtain an inverted egg with a runny white and a yolk that has set.

Although scientifically amusing the inverted egg isn’t really desirable form a culinary viewpoint – the white is a little to runny. Regrettably the formulas presented above aren’t of much help either. They fail because they only take time and not temperature into account. The perfect soft boiled egg in my opinion would have an egg white which is heated to around 70-80 °C and a yolk with temperatures ranging from 64 °C at the yolk-white boundary to about 60 °C in the center. I guess it would be possible to prepare such eggs in a sous vide water bath held at 75-80 °C in less than an hour. A further complication of cooking eggs in real life is that they continue to cook when removed from the hot water. Normally this is alleviated by shocking the eggs in cold water, but if cooked at a lower temperature this could possibly be omitted. I will start experimenting to find a perfect mass-time-temperature combination with a time window that’s as large as possible, and I’ll report the results in a future blog post. And these experiments will also include a test of the recipe for eggs cocotte by Joël Robuchon, found via Chubby Hubby’s post on slow-cooking an egg.

Exotic soft boiled eggs

In his book “Off on a comet”, science fiction author Jules Verne shows that he was actually aware of the possibility of “boiling” eggs at a temperature lower than 100 °C. He has correctly observed that water boils at lower temperature in high altitudes, and that on a fictional comet of appropriate mass, water will boil at 66 °C. The temperature is wisely chosen, because by keeping eggs at 66 °C, you really can’t do anything wrong. From the last paragraph of the excerpt it seems that the eggs were not fully cooked after “a good quarter of an hour”. Of course, there is also no mention about the size of the eggs, so any further speculations end here. But I’ll rather leave it to you to read the excerpt from the Gutenberg e-text version – it’s quite amusing:

The skillet was duly set upon the stove, and Ben Zoof was prepared to wait awhile for the water to boil. Taking up the eggs, he was surprised to notice that they hardly weighed more than they would if they had been mere shells; but he was still more surprised when he saw that before the water had been two minutes over the fire it was at full boil.

“By jingo!” he exclaimed, “a precious hot fire!”

Servadac reflected. “It cannot be that the fire is hotter,” he said, “the peculiarity must be in the water.” And taking down a centigrade thermometer, which hung upon the wall, he plunged it into the skillet. Instead of 100 degrees, the instrument registered only 66 degrees.

“Take my advice, Ben Zoof,” he said; “leave your eggs in the saucepan a good quarter of an hour.”

“Boil them hard! That will never do,” objected the orderly.

“You will not find them hard, my good fellow. Trust me, we shall be able to dip our sippets into the yolks easily enough.”

The captain was quite right in his conjecture, that this new phenomenon was caused by a diminution in the pressure of the atmosphere. Water boiling at a temperature of 66 degrees was itself an evidence that the column of air above the earth’s surface had become reduced by one-third of its altitude. The identical phenomenon would have occurred at the summit of a mountain 35,000 feet high; and had Servadac been in possession of a barometer, he would have immediately discovered the fact that only now for the first time,

as the result of experiment, revealed itself to him–a fact, moreover, which accounted for the compression of the blood-vessels which both he and Ben Zoof had experienced, as well as for the attenuation of their voices and their accelerated breathing. “And yet,” he argued with himself, “if our encampment has been projected to so great an elevation, how is it that the sea remains at its proper level?”

Once again Hector Servadac, though capable of tracing consequences, felt himself totally at a loss to comprehend their cause; hence his agitation and bewilderment!

After their prolonged immersion in the boiling water, the eggs were found to be only just sufficiently cooked; the couscous was very much in the same condition; and Ben Zoof came to the conclusion that in future he must be careful to commence his culinary operations an hour earlier. He was rejoiced at last to help his master, who, in spite of his perplexed preoccupation, seemed to have a very fair appetite for breakfast.

There is in fact no need to head off to other planets to find examples of low temperature prepared eggs. If you go to Japan you’ll find onsen tamago which litteraly translates to “hot spring eggs”. Originally baskets of eggs were lowered into hot springs, but the temperature of hot springs vary so I imagine that there were several types of onsen tamago available (does anyone happen to know the exact temperature of the hot springs used?). After cooking the egg is typically cracked into a bowl of dashi soup with mirin and soy sauce. The challenge of preparing onsen tamago eggs at home is accurate temperature control (just as with sous vide in general). One tip I found was to place the egg on top of rice that has just cooked in a rice cooker. Leave the eggs to “cook” for about one hour while the “keep warm” function of the rice cooker is turned on.

Eggs boiled in onsen (japanese: hotspring), Nagano, Japan (Photo: Miya.m. Permission: GFDL, cc-by-sa-2.1-jp).

I’ve been told that in Finland some saunas are equipped with egg racks. Depending on where the rack is placed one could probably chose between hard boiled and soft boiled eggs. But the sauna would have to be kept warm for a long time due to the slow heat transfer from the hot air. And talking about eggs and saunas: If the eggs are placed directly on the hot stones they will not only be hard boiled, but actually turn completely brown and acquire a nutty flavor. In Korea such sauna eggs are known as Maekbanseok gyeran.

Other aspects to consider when boiling eggs

An egg has somewhere between 7000 and 17000 pores, meaning that water slowly evaporates (the density decreases from 1.086 g/cm³ by 0.0017 g/cm³ daily). This is also why eggs age faster at room temperature than in the fridge. Because of the pores, eggs should not be stored next to foods with a strong smell such as onions (unless of course, you want onion flavored eggs). When boiling eggs it is not uncommon that they crack. The most obvious reason is that they are dropped into the water and hit the bottom of the pot. Another reason for cracking is the expansion of trapped air at the blunt end of the egg. This air cannot escape fast enough through the small pores. Conventional wisdom has it that piercing a small hole in the blunt end will let expanding air escape to avoid cracking. It turns out someone has actually scientifically tested this (with 1000 eggs) and their finding was that there was little cracking for fresh eggs, regardless if they were pierced or not. Piercing reduced the cracking of 5-day old eggs and totally eliminated cracking of 28-day old eggs. The authors theorize that the air pocket grows due to evaporation (meaning there is more air to expand) and that the egg shell of fresh eggs is porous but that the pores gradually become clogged upon storage. Curiously the abstract concludes with the following sentence (this was written in 1973, but it’s still quite unusual for a scientific journal):

Housewives should pierce eggs before boiling them, since if they are fresh it will do no harm and if they are stale it will prevent splitting.

We can safely assume that the advise holds true for men as well! Apart from piercing holes to avoid cracking it is possible to reduce the potential damage from cracking by addition of salt or vinegar to the water. This will help the egg white coagulate faster and thus plug any crack formed.

Picture of egg shell pore (Photo: Jim Ekstrom. Permission: Freeware for non-commercial use).

If you’ve read this far, make sure to also read how the egg yolk problem was finally solved and my follow up post with pictures and a video of egg yolk cooked at 63.0 °C for 40 to 155 minutes!

I recently found an interesting article on how an electric field can be used for maturation of wine (New Scientist news coverage of the article). Applying a AC field of 600 V/cm for 3 minutes resulted in an accelerated aging of wine and according to the authors of the paper, it made “harsh and pungent raw wine become harmonious and dainty”. They observed changes in concentrations of higher alcohols, aldehydes, esters and free amino acids. But I was quite surprised that they don’t say anthing about astringency and polyphenols (tannins). I’d expect some changes there as well, but alas it’s so much more difficult to measure the polyphenols than the low molecular compounds. A sensory panel identified both positive and negative effects of the electric treatment which helped identify an optimum treatment. Apparently several Chinese wine manufacturers are testing the technology on a pilot scale now. Many people have a romantic impression of how wine is made, but the extensive catalogues of “corrective chemicals” available to the modern wine maker should perhaps make you reconsider the romatic idea of wine making. Even professor Hervé Alexandre at the University of Burgundy has given the technology a thumbs up: “Using an electric field to accelerate ageing is a feasible way to shorten maturation times and improve the quality of young wine”. Who knows – maybe you’ll soon be drinking a wine that has been zapped?

Moving from industrial scale wine upgrading to kitchen scale gadgets: In his latest “curious cook” column Harold McGee writes about different gadgets that supposedly can change the flavor of wines. To the better of course. He mentions the Wine wand which is supposed to speed up aeration of wines. The promotional explanation on the web page sounds quite dubious, take for instance the claim that the wine wand can “accelerate the aerating process of wine by replicating the natural frequencies of air and oxygen, and infusing them into the wine”. Complete nonsense! Harold McGee however mentions that he did several blind tests and found that there were differences. I guess we can’t exclude the possiblity that there could be some kind of reactive surface on these wands. From the pictures there seem to be some small (glass?) beads in a hollow cylinder. I can’t find any information about the surface. Perhaps it’s been activated or coated with a metal? In that case we could have plenty of surface chemistry going on. If it’s only glass however – well – then I’d just leave the wine to mature in it’s glass bottle.

The other object he mentions is the Clef du Vin or wine key which is more interesting from a chemical perspective. The active part consists of a metal disc which (in a preferred embodiment to quote the patent jargon) consists of 95% copper, 3% gold and 2% silver. According to the description in the patent application, the device is capable of an “accelerated and gauged oxidation-reduction of the wine”. Dipping the disc into a glas of wine for one second is supposed to equal one year of cellar aging. Metals can catalyze many reactions, and there are many reactive compounds in wine so I wouldn’t be surprised if something happens. Considering the fact that sulfurous compounds (such as hydrogensulfide for instance) are very potent, and that sulfur has an affinity to several metals such as gold, copper and silver it seems plausible that the metal disc may actually remove some sulfides from the wine by adsorption and in turn influence the flavor. However, in the course of one second only a small fraction of the wine has been in contact with the metal disc, so I can’t really see how this should be sufficient. It would in a way be strange if only desirable reactions are catalyzed (i.e. only undesirable compounds are degraded/removed). Anyhow – I’d really like to see a peer reviewed paper on this. For someone with spare time and access to a GC-MS this should be a nice project

A stainless steel “soap” is believed to remove garlic stains from your fingers

Interestingly there is a totally different product that relies on the same chemistry: the steel soap. It is typically shaped like a standard soap bar and consists of plain normal stainless steel. It’s supposed to remove garlic, onion and fish smell from your fingers. It works by rubbing your hands against it under running water. I have one, but to be honest it’s hard to really say if it works or not – perhaps some have more experience with it? I had a friend of mine analyze my stainless steel soap by XPS and he gave me the following elemental composition for the six most abundant elements: 70.6% iron, 18.5% chromium, 8.2% nickel, 1.4% manganese, 0.7% molybdenum and 0.3% copper. This is more commonly known as 18/8 steel where 18 denotes 18% chromium and 8 denotes 8% nickel and it’s what all your forks and knives and other stainless steel tools are made of (which of course means that just about any stainless steel object you have in the kitchen should serve the purpose to remove odor from your fingers). Of the metals present here molybdenum in particular is used industrially for desulfurization of oil. Based on a paper on hydrodesulfurization I speculate whether the mechanism could be something like this:

A proposed mechanism for desulfurization on the surface of a “steel soap”

A sulfur compound exemplified here with a thiol (R-SH) reacts with the steel soap surface and the S-H bond is cleaved. Then the S-C bond is cleaved homolytically to yield radical species. The alkyl radical abstracts hydrogen from the surface and escapes whereas sulfur remains bound to the surface. The surface could be regenerated by removal of sulfur with hydrogen. All in all the chemistry of a steel soap seems plausible to me, but I’m not sure whether the effect is significant effect when it comes to removing that garlic smell from my fingers.

The products of the Maillard reaction provide tastes, smells and colors that are much desired and lend their charachteristics to a variety of foods. In this post I will focus on the factors that influence how fast the Maillard reaction proceeds. And more specifically I’ll give examples on how the Maillard reaction can be speeded up. This is not about fast food, nor is it about saving time. It’s more about controlling the browning reaction by speeding it up or slowing it down in order to get a desired end result.

The Maillard reaction is, to put it simple, a reaction between an amino acid and a sugar (there’s more on the chemistry at the end of the post). To speed it up you can do one or more of the following:

Chances are you have already utilized this in the kitchen without knowing. When eggs or milk are used for glazing, they act as a protein source for the Maillard reaction, giving a nice brown color. Milk also provides lactose which is a reducing sugar. You’ve probably also observed that temperature does influence browning. Water content is indirectly related to temperature – as long as there is water present, temperature will stay below 100 °C. But once the bread crust dries out the conditions are just right to get the Maillard reaction running.

The same principles are applied to microwaveable pies. The microwaves primarily interact with water and hence only bring the temperature up to the boiling point of water. In order to get sufficient Maillard productcs at these temperatures reducing sugars and amino acids are added to the crust (as exemplified in this patent where dextrose and whey solids are used). Not so surprisingly there is also a patent on how to avoid excessive browning in cookies which calls for addition of a polycarboxylic acid ester to lower pH and hence slow down the Maillard reaction.

Pretzels are an extreme example of how the Maillard reaction can be tweaked. Before baking the pretzels are brushed with lye, a dilute solution of sodium hydroxide, which is very basic. The high pH speeds up the bottleneck of the Maillard reaction (see end of post for details).

A pinch of baking soda can bring out a new taste dimension when browning onions

Another basic ingredient found in most kitchens is baking soda (sodium bicarbonate, NaHCO₃). It’s used as a leavning agent which requires addition of an acid to function. Since it is a weak base, it can be used to increase the pH and hence the speed of the Maillard reaction, for instance when browning onions. This basic task, which isn’t always so easy after all, benefits greatly from a pinch of baking soda (and surprisingly it seems that this hasn’t been done before!). To illustrate this I’ve made a time lapse video of chopped onions being fried with and without baking soda. The frying took 11 min, but things are speeded up about 10x.

Samples taken throughout the experiment are shown in the picture below. Even after 4 min there is a visible difference. After 11 min, the small addition of baking soda has yielded onions which taste remarkably sweet with strong caramel notes, compared to the control which tastes like fried onions.

Another example of how baking soda is used to speed up the Maillard reaction is dulce de leche, a popular sauce/caramel candy in Latin America. It’s made by slowly boiling sweetened milk. Baking soda is not a required ingredient, but is often included. The baking soda gives dulce de leche a darker color and also contributes to the flavor.

Photo by audinou from flickr.com.

It should perhaps be added that baking soda is frequently used in Chinese cooking, for instance in tempura batters and marinades. Once there, the baking soda will certainly speed up the Maillard reaction, but it also affects the texture of meat – I’ll have to return to that topic later.

To round of this post I will briefly touch upon one of the reasons why pH influences the Maillard reaction. The first step involves a reaction between a reducing sugar (depicted as R(C=O)H) and an amino acid (depicted as R’NH2) followed by loss of water to yield a Schiff base. The Schiff base rearranges to the Amadori product (not shown). Of these first steps the formation of the Schiff base is the bottleneck (rate limiting step). The reactivity of the amino acid is influenced by the pH. A simplified reasoning goes like this: At low pH the amino group is protonated, yielding it less nucleophilic. At higher pH, the nitrogen becomes more nucleophilic and at very high pH the amino group can even be deprotonated. It should be noted that the fate of the Amadori product is also in large determined by pH and hence pH will affect more than just the rate, but this is far beyond the scope of this blog post.

The soda fountain (Diet Coke + Mentos) has been around the net for quite a while with some spectacular videos available, and it has even made it into a news paper cartoon. People go crazy about this and the largest number of simultaneous fountains is steadily increasing.

Despite the interest, only now did a scientific paper appear on the subject. Many have speculated about what causes the reaction between Mentos and Diet Coke, and some have focused on possible acid-base reactions taking place. Mythbusters investigated this in 2006 (watch episode) and came up with the following factors that contribute to the bubble formation:

Diet coke

• carbon dioxide is what makes the bubbles form in the first place
• in synthetic mixtures aspartam, caffeine and potassium benzoate where shown give better fountains

Mentos

• the most important property is the rough surface which provides plenty of nucleation sites for bubble formation
• the density makes them sink which is ideal as the bubbles formed at the bottom of the bottle help expel much more soda
• mentos contains gelatin and gum arabic which could also reduce surface tension

In the paper “Diet Coke and Mentos: What is really behind this physical reaction?” by Tonya Shea Coffey the findings of the Mythbuster teams are largely confirmed.

By measuring contact angles it was shown that aspartame and potassium benzoate reduce the surface tension of water. Aspartame is a winner, and as an extra benefit clean up is much easier with Diet Coke than sugared Coke. The amount of caffeine however is too low to have any effect. The roughness of the Mentos surface was studied with special microscopes (see picture below). Fruit Mentos have smooth patches, but the coating is not uniform and contrary to the Mythbuster experiment normal Mentos and Fruit Mentos performed equally well with regards to foam formation. The roughness of the Mentos surface was inbetween that of rock salt and the Life savers which suggests that roughness is not a single factor determining the reaction. The Mentos surface is covered with gum arabic which reduces surface tension, and experiments showed that even without Mentos, gum arabic could cause a reaction to occur. It is the combined effects of reduced surface tension (due to ingredients in Diet Coke and Mentos) and the rough surface of Mentos which is the key to understand the reaction.

As expected, the article also confirms that the reaction is more vigours at higher temperatures (i.e. solubility of carbon dioxide deacreases with increasing temperature). It was also shown that Mentos sink faster to the bottom of a 2 L bottle compared with rock salt, Wint-O-Green Life savers and sand (this is a function of size and density, not only density). When bubbles are formed at the bottom of the bottle the bubble has more time to grow as it rises. This causes a more explosive reaction and more soda is expelled from the bottle.

The picture shows scanning electron microscopy images of Mint Mentos (a) and (c) and Fruit Mentos with a candy coating (b) and (d). The scale bars in each image represent the lengths (a) 200 μm, (b) 100 μm, (c) 20 μm, and (d) 20 μm. Fruit Mentos has smooth patches, but the coating is not uniform. (Reprinted with permission from Coffey, T. S, American Journal of Physics, Vol. 76, Issue 6, pp. 551-557, 2008. Copyright 2008, American Association of Physics Teachers)

The question which lingers on my mind is whether Diet Coke and Mentos represent the optimal combination of ingredients to create a soda fountain. With regard to convenience, I guess the answer is yes. But perhaps it’s possible to create an even more powerful reaction? Since lowering the surface tension of water is important, I’m wondering if it would be possible to find a surfactant that could be added without setting the reaction off? Mentos would of course still be needed for the rough surface to provide nucleation sites. In the above mentioned study addition of diluted dish washing liquid was enough to give a pretty good reaction, so this is not an option. But perhaps a couple of drops right on the Mentos surface would work? I definitely need to try this some time.

Ethanol is a molecule with both a polar and a non-polar end, so it’s properties are somewhat in between those of water and oil (which will be the topic of the next post in this series about extraction). This is easily illustrated by the fact that both water and oil are soluble in pure ethanol (albeit not at the same time – adding water to ethanol reduces the solubility of oil). Many taste molecules are polar whereas most aroma molecules are non-polar, and the good thing is that ethanol can be used to extract both groups of compounds.

I belive the most widespread use of ethanol for extractions in the kitchen is for sweet liqueurs where fruits or berries are extracted with ethanol and the extract is sweetened with sugar. The word liqueur comes from the Latin word liquifacere which means “to dissolve”, and this is essentially what happens – the ethanol and water extract and dissolve flavor and color from the fruit.

Some also make their own spirits by infusing spices and herbs. One example is aquavit which is based on carraway combined with a number of other spices for complexity such as dill, coriander, anis, fennel, liquorice, cardamom and lemon. Commercial aquavits are distilled, but at home it’s suffices to filter of the spices and herbs. As a result home made aquavits are always amber colored (such as the one pictured in a previous post).

For extractions like these, one always uses diluted ethanol, typically 30-60% ethanol in water would be used, and most often somewhere around 40-50%. One reason for this is that higher concentrations of ethanol would extract to many bitter and astringent compounds. Another reason is that in some (most?) countries it is illegal to posess, buy and/or sell ethanol at higher concentrations for consumption (pure ethanol for technical use is denatured if sold in normal stores and requires special permissions if used in laboratories).

Apart from the steping herbs and spices in ethanol to make liqueurs, the only other example of relevance for the kitchen I can think of is for extraction of vanilla beans to make pure vanilla extract. This is quite surprising actually, and although I really don’t know if ethanol is used for extraction in professional kitchens, it is my impression that ethanol extractions are underutilized in the kitchen.

There are several benefits with ethanolic spice and herb extracts:

• fast – no need to wait for the spices to be extracted since they have been “pre extracted”, you can taste the dish immediately and add more spice extract if necessary
• no residues – seeds, leaves or bark are filtered off before use
• convenient – spice extracts are an excellent way of adding clean, concentrated aromas
• stable – spice extracts keep very well (although the storage may also change the flavor profile somewhat and “mature” the flavor)
• new flavors – some spices and in particular herbs will change upon extraction and storage and this can open up new possibilities (this needs quite some experimentation though – some herb flavors change to the worse…)

What are your experiences with ethanol extractions in the kitchen?

Water is a polar molecule, meaning that one end has a small negative charge and the other a small positive charge. Because of this water is a very good solvent for other polar molecules and ions. For instance water is the solvent of choice for substances that provide taste, be it salt, sour, sweet or bitter as these are normally quite polar molecules.

A general rule is that the solubility of molecules and ions increases with the temperature of the water. Extractions are therefore faster if the water is boiling. This is the reason why we use hot water to extract tea leaves or ground coffee beans, even if we want to prepare ice tea or ice coffee. But by lowering the temperature and extending the extraction time we can change the relative proportion of what we extract. It therefore makes perfectly sense that different temperatures are recommended for different types of tea. Using different temperatures for the same kind of tea will of course also influence the flavor profile.

Polar molecules are more easily extracted than non-polar molecules. This is evident if we leave a tea bag for a long time in hot water. The bitter taste is due to the slow extraction of large polyphenol molecules which are less soluble in water. If tea is brewed at a lower temperature, less of the bitter tasting substances will be extracted.

Although water is polar, less polar and even non-polar substances can be extracted with water, especially if the water is boiling hot. You do this every day when prepare coffee. If you take a close look at cup of freshly brewed coffee you can notice small pools of oily substances floating on top of the coffee. The more severe conditions used when extracting coffee to make an espresso ensure that even more oily substances are extracted. Other examples of extraction using water in the kitchen include preparation of stock, soups and gravies.

The principle of extraction is simple, but a number of questions remain largely unexplored with regard to flavor: How do ions affect extraction? What role does pH play? How does temperature influence flavor? There is surprisingly little research on this that includes a sensory evalution.

For the following experiment I purposly left some lettuce (Lactuca sativa var. crispa, sold in Norway under the name “Rapid”, it’s a Summer Crisp/Batavian cultivar) to really dry out as you can see from the picture.

After approximately 4 hours in water the leaf looks like this. Notice that along the rim the leaf was so dry that the cells were damaged “beyond repair”.

To illustrate this relatively slow process I set my camera to take a picture every minute and left it for almost 4 hours. I then stiched it together and the resulting time lapse movie shows the process speeded up 720x (click if the embedded video won’t work).

The wonderful thing about this simple experiment is that it actually illustrates the essence of a recently rewarded Nobel prize (and I should thank Erik Fooladi for pointing this out to me)! The 2003 chemistry prize was awarded “for discoveries concerning channels in cell membranes”. The swedish Nobel foundation have excellent pages with further explanations for the public and for specialists alongside an illustrated presentation (recommended!). There are even two animations of which the first is also available on youtube (embedded below, poor resolution, download the original for higher resolution!). It shows how water molecules move through cell membranes:

8. Experiment!

Dare to experiment and try new ingredients and procedures. Do control experiments so you can compare results. When evaluating the outcome, be aware that your own opinions will be biased. Have a friend help you perform a blind comparison, or even better a triangle test to evaluate the outcome of your experiments.

In a scientific context, an experiment is a set of actions and observations performed in the context of solving a particular problem, in order to support or falsify a research hypothesis. In a kitchen context, the problem to solve would typically be related to taste, aroma, texture or color. And the required actions and observations would be cooking and eating.

An essential part of the scientific method is that new knowledge is gained when, based previous knowledge, an assumption is made and tested. In the kitchen, this is exactly what you do when you taste your concoctions repeatedly as you cook. And it is also what makes you an experienced cook, because you remember and learn from your previous successes and mistakes. It might sound very complicated, but here’s how it goes:

1) Observation: soup lacks flavor
2) Hypothesis: adding something with flavor might help
3) Experiment: add more spices
4) New observation: soup tastes more (or less)
5) Hypothesis is either supported (or rejected)

Of these steps, I think observation is the easiest. Coming up with a hypothesis however can sometimes be difficult. If you have lumps in your custard or a sauce that’s separating, it isn’t always easy to think of what to do. This is where books on popular food science and molecular gastronomy might help you.

Think outside the cook book! I mentioned in previous post that you should always question authorities and cook books. And even when you have a recipe that works, remember that it’s nothing more than a suggestion. For instance, it can be useful to know when to be sloppy and when to be accurate with measurements. The smaller amount you measure, the greater the precision should be. Let’s consider a hypothetical recipe that calls for 1000 g flour and 1 g of saffron. Whether you use 999 or 1001 g of flour makes no difference, but using 1 or 2 g of saffron will be quite noticable. A good rule of thumb is that you should measure to within +/- 10% of the given amount. But again, don’t follow this blindly. Experience will show when you can be even more sloppy.

Thinking of good experiments to do requires both creativity and experience, and there are many sources of inspiration. The molecular gastronomy movement has come up with a number of books and blogs which point towards new ingredients and procedures. There are several approaches to flavor pairing (i.e. a general one based on experience and a chemical one based on impact odorants). Further more there’s a lot of inspiration to get from regional cooking – also for molecular gastronomists! Lastly, I think considering not only the food but the whole atmosphere and the setting of the meal is important, because our senses are connected!

The best way to judge the outcome of a new procedure or ingredient is to compare it with the original. I’ve previously termed this “parallel cooking”. In scientific contexts it’s very common to do control experiments and I can’t see why this shouldn’t be done in the kitchen routinely. Im convinced that this could have saved us from many kitchen myths!

Once you’ve done your parallel cooking, you have to taste it. If you did the cooking, you’ll probably have an opnion or expectation that the new dish is better or worse than the original. The big problem here is that due to confirmation bias, if you know what you are eating, this will influence your perception of it. Therefore it’s crucial to do a blind tasting (or a double-blind tasting). Have friend help you label each dish with random three digit numbers (to avoid thinking about ranking) and give them to you. If the dishes can easily be recognized due to color, it’s important that the lights are turned down or that you are blindfolded. State which dish you prefer and have your friend reveal the identity of the dishes tasted.

A slightly more sophisticated test is the triangle test which is commonly used in the food industry. The tester is presented with three samples of which two are identical and the task is to pick the odd one out. Using statistics, it’s possible to evaluate the outcome of repeated tests. The number of correct assignments in a number of triangle tests required for you to be 95% sure there is a difference are given in the table below. Read more about simple difference tests here.

Bionomial distribution for a triangle test (p=1/3) at 0.05 probability level. A more extensive table can be found here.

It seems that this would be the ultimate way to determine whether or not there is a difference between pepsi and coke. It’s more than 50 years since the first experiments were conducted. The theory is simple, but in the real world things aren’t always that simple. Read the entertaining story about Fizzy logic.

There are several examples of experimental cooking out on the net, and I thought I’d share some of them with you as this might illustrate my ideas on the subject.

Many cooks have strong opinions about how garlic should be treated. Should it be minced, crushed or microplaned? And does this really influence the taste and aroma? Or does it only affect the degree of extraction and hence the intensity of the flavor? Dominic of Skillet Doux had a excellent post on this subject in 2006, Deconstructing garlic. The task was formulated as follows:

The subject of this experiment is the effect that various methods of breaking down garlic have on its flavor when used to prepare a dish. The hypothesis is that not only does mincing garlic create a different flavor than crushing it, but also that mincing is the preferred method for pasta sauces. Furthermore, the experiment is intended to determine if microplaning garlic achieves a character different from mincing or crushing.

In his conclusion, Dominic writes ” I was surprised to discover that the difference between the minced and crushed garlic sauces was even more significant than I had previously thought”. Check out his post to find out which kind of garlic treatment he prefers for his pasta sauces. As a side comment it can be mentioned that a group of researchers in 2007 studied the effect of cooking on garlics ability to inhibit aggregation of blood platelets. They found that crushing could reduce the loss of activity upon heating. But unfortunately they didn’t report anything about the flavor.

Other food bloggers have also adopted experimental cooking with emphasis on systematic and thorough testing. Examples include Chad’s experiments with gellan, konjac and iota/kappa carrageenans, Michael Chu’s parallell cooking of bacon and his eggplant test and Papin’s comparison of orange juices – to mention but a few! And I shouldn’t forget Dylan Stiles either whom I mentioned in part 5 of this series:

A challenge with aroma molecules is that they should remain intact during storage and not be released until cooking (or even better, until consumption). A example would be to install a Liebieg condenser over your pot. Dylan Stiles has explored this in his column Bench Monkey by placing a bag of ice on top of the lid. He claims that his roommates preferred the curry which has been cooked under “reflux conditions”. The study was performed in a double blind manner (which I will come back to in part 8 of this series).

An extreme example of the application of the scientific method to cooking appeared in the news last spring when the recipe for the ultimate bacon buttie was revealed by scientists from Leeds University. Commissioned by Danish Bacon, the study evaluated more than 700 variations of a bacon buttie. They even came up with a “formula” for the perfect bacon buttie and quantified the required crispiness and crunchiness. The news story was picked up by many news agencies, so although it wasn’t necessarily ground breaking science, at least it was clever marketing.

*

Check out my previous blogpost for an overview of the 10 tips for practical molecular gastronomy series. The collection of books (favorite, molecular gastronomy, aroma/taste, reference/technique, food chemistry, presentation/photography) and links (webresources, people/chefs/blogs, institutions, articles, audio/video) at khymos.org might also be of interest.