OK, so you have some Sodium Hydroxide (NaOH) solution that you have been using to measure your sake or wine’s acidity but it has been a while. Maybe even a long while. You want to make a measurement but will it be accurate? Will it have absorbed too much CO2 to give an accurate measure? How do you know? Well, with a dilute solution of Hydrochloric acid (HCl), 0.1 molarity is good, you can answer your questions and get back to the task at hand.
Unlike Sodium Hydroxide, Hydrochloric acid is stable so it can be stored and used over a long period without degradation. This stability makes HCl ideal for determining the actual concentration of your NaOH solution.
Using HCl to determine the concentration of NaOH depends on the reaction:
Acid and Base to Salt Reaction
which converts an acid and a base to water and a salt. This reaction along with the following equality can be used to determine the actual concentration of the NaOH solution if we have accurate knowledge about the other values.
Basic Concentration Equilibrium
Knowing the HCl solution molarity (0.1 for our work) and using a specific sample volume of the HCl solution (say 10ml) along with the fact that the molar ratio[1] in the above reaction is 1:1 leaves only the NaOH volume to be determined in order to calculate the NaOH concentration. Let sample1 be the HCl and sample2 be the NaOH. This gives:
Filled in known values
so
Rewritten for concentration
or
And Simplified
Given this, if we titrate to neutralize 10ml of a 0.1 Molarity solution of HCl and it takes 11ml of your NaOH solution to neutralize the HCl then the molarity of the NaOH solution is 0.0909… M or about 0.091 M. Now that you know the molarity of the NaOH solution that you are using, you can substitute this value into the equation you are using to determine the acidity of your sake while following the standard titration procedure.
One additional benefit of being able to determine the molarity of your NaOH solution is that you can actually make your own. With this you are no longer dependent on your lab supply store for NaOH solutions with an accurately known molarity. The mole mass of NaOH is roughly 40 grams. So to create a 0.1 molarity solution of NaOH we start with 1 liter of distilled water and add 4 grams (0.1 x 40) of NaOH granules. This gets us very close to the 0.1 molarity solution we want but with the accuracy of our equipment it is not close enough. With the above procedure we can get the needed accuracy.
[This article is related to the "Measuring your sake" series which starts here]
[1] That is, one molecule of HCl to one molecule of NaOH is all that is needed to allow the reaction.
In part one I talked about how to measure the Nihonshu-do or Sake Meter Value (SMV) or your sake. In part two I covered how to measure the Arukoru bun (アルコール度数) or Alcohol percent by volume (%ABV). In part three I covered how to measure the sando or acidity of sake. In this part, part 4, I will cover how to measure the amino sando of your sake.
As is the case for measuring the sando, you will need some Sodium Hydroxide (NaOH) solution usually at a concentration of 0.1 Molarity (M), phenolphthalein, a small beaker to mix the sample and chemicals in, and a syringe to measure with. All of this can be purchased as a wine acid test kit. In addition you will need some formalin[1] solution. As is the case in measuring sando, you can use the phenolphthalein as an indicator or a pH meter to determine the point at which the pH reaches 8.2.
The method used to measure the amino sando is very similar to the method for measuring sando. In fact, it incorporates the sando method as the first step in measuring the amino sando. This is because amino sando is just a specialized acid that is locked up and hidden in the structure. To measure the amino sando we must first remove or neutralize other acids so that they are not counted along with the amino acids. This is accomplished in the first titration step which determines the amount of base require to neutralize the acid. After our sample solution has been neutralized there are no more extra H+ to worry about and we can focus on how to make the amino acids visible, or at least measurable in some fashion. This is done with a formalin solution. The formalin solution reacts with the amino acid freeing an H+ from each amino acid structure. This free H+ can then be locked up using a base just as we did to measure the acid levels. So, one more round of titration using our base solution, sodium hydroxide (NaOH) will give us the level of base needed to neutralize the newly exposed acid so we can calculate the amount of amino acid as glycin, the simplest amino acid.
If that seems a bit intimidating, don’t worry, we will take it step by step from here.
OK, first we need to measure out 10ml of sample sake to evaluate. Place this in a beaker and add a few drops of phenolphthalein. The drops are not needed if you will use a pH meter. Load the syringe with about 10ml of NaOH and record the exact amount in the syringe for later reference; call it R1.
At this point, it is time to add, drop by drop the NaOH from the syringe to the sample watching for the indicator to change color to a light ping for at least 30 seconds. Swirl the sample after each drop as you go. If on the other hand you are using a pH meter you should gently stir the sample with the meter probe to get a correct reading. Once the color changes and holds its light pink color for at least 30 seconds you have neutralized the sample. Record the NaOH level now present in the syringe; call it R2. The difference between this and the earlier recorded level, (R1-R2) can be used to determine the sando (acidity).
Up until this point the procedure has been the same as measuring the sando. It is at this point that we depart from the sando method. Set the neutralized sample aside for use once we have a mixture based on the formalin ready.
Mix 50ml of formalin with 50ml of distilled water. Using the same titration procedure, neutralize the mixture at a pH of 8.2 or where the indicator turns light pink for at least 30 seconds. Remember to add several drops of phenolphthalein if you are using the indicator. There is no need to record the amount of NaOH used for this procedure.
OK, we are ready for the final step. Measure 10ml of the neutralized sample and 10ml of the neutralized formalin mixture and place in a beaker for a total of 20ml. Reload the syringe with NaOH and record the amount contained; call it R3. If you have been using phenolphthalein there should be enough present without any addition. Titrate this 20ml sample until it reaches neutrality at pH of 8.2 or until the color changes to a light pink for at least 30 seconds. Record the final level of NaOH in the syringe; call it R4. The difference between this and the previous recording will be the amount of NaOH required to neutralize the amino acid; (R3-R4).
Having completed all the measurements, it’s time to calculate the levels. First, as before for sando:
Where the BaseMolarity is the concentration (moles / liter) of NaHO in distilled water, BaseVolume and SampleVolute are the amounts of NaHO and Sample solutions in ml.
Succinic acid, along with malic and lactic acid are the most abundant acids in sake. As discussed in part three, succinic acid has a reaction ratio, MoleRatio, with NaOH of 1:2 giving rise to the ½ in the Sando equation. The amino acid glycin reacts with NaOH in a 1:1 reaction giving rise to the multiplier 1 in the Amino Sando equation.
The molecular mass (MoleMass)of succinic acid is 118 while the molecular mass of glycin is 75. As you see, these have been substituted in the equations above.
Using a pH meter can be slower and more tedious than using phenolphthalein but the pH meter will be more accurate. In either case, any amount that you are off on any of the titration steps, first for sando, second for formalin or the final step for amino sando, will throw off the following step or be thrown off by the previous steps; that is, the error will accumulate with each step.
Another thing that should be understood and kept in mind when working with NaOH is that its concentration will change over time. NaOH reacts with CO2 in the air neutralizing its base character. You can use Hydrochloric acid (HCl) to determine the strength of the NaOH solution. HCl is stable so, while NaOH is changing, HCl will remain constant and able to measure the new/ current strength of the NaOH concentration using the same titration methods used above. Maybe I will discuss this in more detail in a future article. [12-10-11, well I added a post on this. You will find it here]
Well, there you have it, the procedure to measure the sando and amino sando of your sake.
[1] Formalin is a saturated solution of formaldehyde at 40% by volume or 37% by mass.
Well over a decade ago, I became smitten with nihonshu at NYC sake bar and drinking institution, Decibel.
I didn’t know it at the time, but my experience there–its hidden-away, speak-easy location; a secret grotto showcasing a depth of sake that I had no idea existed–would lead me on a pilgrimage to learn more in Japan and eventually to brewing sake commercially.
In January 2006, I travelled to Kamakura where I met eight other foreigners interested in sake. We gathered at a local art space to learn and discern the drink with John Gauntner, preeminent American sake expert and author, who has lived in Japan more than half his life.
Blake, Elise and John at moto-i
Little did I know I was in the company of several pioneers who would spread the gospel of sake to their respective cities and countries in the years to come. Among them was Nancy Cushman, my tatami mat buddy. She and husband, Tim, would later open Boston’s o-ya, one of the best modern Japanese restaurants in America. Johnnie Stroud was in attendance, before he and wife, Taiko, opened Sake Nomi—a premium sake retail shop in Seattle. Kjetil Jikiun owned a micro-brewery in Norway called Nogne-O, which gained considerable traction in recent years with the craft beer boom. Kjetil dreamt of making sake, and last year began brewing “Hidaka Jima” at Nogne-O’s facilities. And there was this guy named Blake Richardson, who owned a brew pub and had lofty ideas of creating the first sake brewery restaurant outside of Japan—in Minneapolis, Minnesota. Continue Reading »
OK, so the bodai moto based sake I am working on, rested for about 1 month after pressing. Normally, I would have racked it after a couple of weeks but the lees were just not dropping out. I have not had a sake that was so slow to drop its leas before. After one month the sake appeared as in the picture below:
Bodai-moto One Month After Pressing
Not very encouraging in turns of being able to recover a large percentage of the sake as clear sake. Anyway, I had been thinking about filtering sake and thought that this maybe a good batch to give it a try with. You may recall that the fermentation went very slow and I pressed it too early despite it having had more time to ferment than most. The moromi went through stages of smelling like green apples, strawberries and finally banana’s. These aromas have been very strong and are very evident the minute I open the cooler. At one month after pressing the banana aroma continues to be very strong; Ginjo-ka on steroids.
The equipment I used for filtering consists of a 5 gallon Cornelious keg, and a plate filter with a 7 micron filter paper. I also have 3 micron and 1 micron filter paper but I was afraid that the filter would clog and I would lose too much sake. As it turned out the filter was very close to being clogged if not actually clogged at the end of pushing about one gallon of sake with leas through it. The following picture shows the front and back sides of the 7 micron paper filter and the back plate of the filter housing. Continue Reading »
We have just added the Akita Konno “Special Ginjo” koji-kin to our offerings in the store. This new koji-kin has been developed at one of Japan’s leading koji-kin suppliers specifically for making Ginjo sake.
Unlike most koji-kin available for homebrewers, Akita Konno’s special ginjo koji-kin is specifically for making sake. We provide two 1 gram packets, each of which will make more than 3 lbs. That’s enough for two standard batches of sake.
The instructions provided have been reviewed by Akita Konno to insure the information given meets their high standards.
This week I thought that it would be interesting to look at the rice production in the US. This quick look will actually be narrower than the whole of the US in that I am using material exclusively from the Sacramento Valley in California. However, many of the themes will be true for the US and are in stark contrast to what we often see related to rice for sake, our primary interest.
I have been watching the youtube channel RiceNews for a couple of years now and find it to be very interesting. All of the videos here have been selected from their offerings.
While the rice farming families in the US can’t go as far back as those of Japan can, many of those in the Sacramento Valley go back to the beginning of California production.
In the following, I have pulled together views into each stage of rice growing. There was nothing on drying, husking, milling and bagging so that is a missing piece. Maybe I can fill that in some time in the future. Continue Reading »
Today, Nihonshu no hi or international sake day, is not only a day to celebrate sake but, beginning this year, also the opening day for a new kura, sake brewery, in the great state of Texas. Texas Sake Company becomes the 7th currently active US sake brewery.[1]
Using a strain of organic Texas rice that is said to have a heritage that traces its roots back to rice from a Japanese delegation that came through Texas in 1904, The Texas Sake Company will specialize in local organic ingredients. Yoed Anis, the founder and Toji of Texas Sake is truly excited about using Texas grown rice with roots that go back to Japan.
Texas Sake has actually been operating for some time while getting ready for the grand opening, October 1, 2011. They began at least as early as February to produce test batches of sake which they gave away to their followers in Texas; a nice way to build the following. Their grand opening is being held at the brewery: 5501 N Lamar Blvd, A115, Austin, Texas.
It is wonderful to see a new kura starting up; welcome Texas Sake Company.
[1] I have documented the other US sake brewers here.
I have just completed the pressing of a sake made with a bodai moto and while the story is still not complete I think this may be a good time to look at what we have so far. The bodai moto is the original method of creating a moto. As I have written before in this venue, the bodai moto was created from a sake brewing method known as bobaisen. Bodaisen was sake made using the same method used for bodai moto but there is no additions added later. For bodaisen you put all the ingredients together at the beginning and then ferment to the end with no additions. Over time it was found that adding a bit of the mash of a good brew to the beginning of a new brew helped make better sake as well as make it more reliable. As the properties of the sake improved while adding a “starter” from a good batch, this became the norm and even the first batch needed to have a starter and this push for better sake is how the method for making bodaisen became the method for making bodai moto.
Bodai moto is also called mizumoto or water moto. The name mizumoto makes a lot of sense once you begin to look at the method used and what it produces. The outcome of the first step of the method is a special water called soyashi-mizu that contains, along with the water, lactic acid that will protect the moto and the ferments made with this moto. There are also other compounds from various bugs that became active before there was enough lactic acid to kill them off. These bugs and their effect on the moto bring distinctly different contributions to sake. Similar to yamahai moto sake, bodai has its own funk.
To start a bodai moto we need to make the soyashi-mizu. Soyashi-mizu is created in the soyashi process which consists of mixing a small amount of cooked rice with raw rice and water and letting stand until the lactic acid reaches the desired strength. Now I should say that in the original process this is also key to cultivating a good yeast population. Because I will add yeast I am not really looking for this but it may also be a strong contributor to the resulting characteristics. Continue Reading »
Nøgne ø, I believe is the first craft beer brewery in Norway and would make any US microbrewery proud. They, led by Kjetil, have been making outstanding brews. They have been very open with the Homebrew community so much so that Kjetil described how to clone his beers in an interview with the Brewing Network to be made available as part of the “Can you brew it” podcast series. One such episode is on Nøgne ø Porter.
Kjetil and True Sake, in an effort to raise more funds for the Japan relief, put a full flight of Hadaka Jima up to the highest bidder. I was excited to hear about this because Kjetil’s sake is not yet available in the US for purchase and I have been watching his progress from the time he first signed the contract to buy rice from Hokaido. I quickly sent in my bid and sat back for what I expected to be around a month before the bid would be complete. As it turned out, I got lucky and won the bid. Now, with 6 Hadaka Jima in my refrigerator I am ready to see what Kjetil and his team have created. I am really excited.
NØGNE-Ø Full Sake flight
The rice used for these brews is Yamada-nishiki, Ginpu or both, all with a 70% seimeibuai. Continue Reading »
One of the first things we did while in Japan was to visit Yasutaka Daimon the owner and Toji of Daimon Shuzo. He is an incredibly nice and warm man who made us feel extremely welcome. During our visit I captured some video that I like but am a little embarrassed by. The quality and choice of where I was pointing and not pointing the camera could have been much better. Well, live and learn. I hope you find them interesting despite the quality.
This first video begins while we are talking about the moisture content of the rice prior to steaming. Yasutaka-san says that they shoot for a moisture content of 32-33% for the rice that will be used to make koji and 28% for the rest of the rice, the kakemai (掛米).
