Wednesday, September 25, 2019

grammar - Meaning of noun + だったりする



すごく背が低いけれど、いつも堂々とした態度で、颯爽とした雰囲気がある。



そして――‥‥彼女は僕の彼女だったりする。



What exactly is the meaning of "だったりする" here? I've read in A Dictionary of Basic Japanese Grammar by Seiichi Makino that when たり is used with adjectives and nouns, it means "sometimes". Accordingly, when I first read the above line, I understood the part in question as "She is sometimes my girlfriend(and sometimes not)". Is that the correct interpretation? From context, it doesn't feel like it is so. Is there another way of understanding "だったりする"?




physical chemistry - Can we define a new unit instead of specific heat that is constant with temperature rise?


Specific heat plays an important role in calculating energy and thus, heat, enthalpy and etc.
But as I sighted the definition for calorie, I was surprised.




A calorie is the amount of heat needed to alter the temperature of 1 gram of 14.5 °C water to 15.5 °C water in the pressure of one atmosphere.



Though the unit was redefined later, the question remained still. Why were there those temperatures? It was just then that I realized specific heat capacity varies with temperature differences and it is due to vibration movements of matter and internal energy ....
Two questions: Can there be a unit which is constant with temperature alterations that can be used instead of S.heat capacity? If so, why isn't it replacing SHC?
The resource for the quote
The resource for the reason of the increase that happens to SHC with temperature rise



Answer



There isn't a simple redefinition that would work in all cases, and this is probably why nobody does this. Of course, you COULD define such a unit for a given system by defining it as a function of temperature, but it would be applicable only to the specific system.


As you noted, the physics behind the temperature dependence of a material's heat capacity lies in the quantum states which become available for excitation at different energies. Consider an insulator which stores heat primarily in the lattice vibrations. As you increase the temperature, more vibrational modes are accessible. This is often described using the Debye model which gives the heat capacity as such:



$C_V = k(\frac{T}{\theta})^3$


where $C_V$ is the heat capacity, $k$ is a constant, $T$ is the temperature in Kelvin, and $\theta$ is a constant pertinent to a specific solid.[1]


However, a metal can also store a significant amount of heat in the motions of electrons since conduction electrons are not bound to specific sites. Heat capacity for the electron 'gas' is often described like this:


$C_V' = k' \frac{T}{\theta'}$


where $C_V' \neq C_V$, $k' \neq k$ and $\theta' \neq \theta$.[2] Depending on $\theta$ and $\theta'$ for a given material, at low temperatures (often cryogenic) the electron contribution can be the dominant mode of storing heat in the solid. Thus, if you chose a unit which was sensible for an insulator, it wouldn't apply to a conductor (and vice versa).


Even within a specific material, the heat capacity on either side of a phase transition is often different since the phase transition has changed the quantum states available in the material. Therefore, your new unit would become discontinuous at phase transitions and would need a different mathematical expression for each segment of the heat capacity function, not to mention a different parameterization for each material. Hence, no real gain.


[1] See Kittel, Kroemer, Thermal Physics Second Edition; W. H. Freeman and Company, New York, 1980, p. 106, eq. 47b


[2] See Kittel, Kroemer, Thermal Physics Second Edition; W. H. Freeman and Company, New York, 1980, p. 193, eq. 37. Note that folks don't actually use the symbol $\theta'$ in this case, but choosing so makes the explanation above clearer.


physical chemistry - Prove that a 10-Degree Temperature Increase Doubles the Rate Constant (k), when the Activation Energy is Approximately 50 kJ/mol


I read that increasing the temperature by $10~^\circ\mathrm C$ will double the rate constant ($k$), when the activation energy for the reaction is relatively close to $50~\mathrm{kJ/mol}$.


However, no matter how hard I try to wrap my head around it (through graphical examples that require plotting the natural logarithm of $k$ vs the inverse of temperature), I just can't grasp this so called "rule of thumb".


As a result, I tried proving this statement through mathematical expressions:


(Note that the activation energy was evaluated for $50\,000$ because it needs to be expressed in $\mathrm{J/mol}$ to be used in Arrhenius' equation)


Prove that...



A rise of temperature of $10\ \mathrm{^\circ C}$ will double the rate constant, when the activation energy for the reaction is approximately $50\ \mathrm{kJ/mol}$.




Proof starts here -----------------------------


For: $\Delta T = T_2 - T_1$ ($T_2$ is the final temperature, and $T_1$ the initial temperature)


When: $\Delta T = 10 \rightarrow T_2 - T_1 = 10$


It follows that: The ratio between $k_2$ (at $T_2$) and $k_1$ (at $T_1$) will equal $2$, owing to the doubling of the rate constant ($k$):


$$ {k_2\over k_1} = 2 $$


Employing Arrhenius' equation:


$$ {k_2\over k_1} = {A\mathrm e^{\left({-E_\mathrm a\over RT_2}\right)}\over A\mathrm e^{\left({-E_\mathrm a\over RT_1}\right)}} = \mathrm e^{\left[{-E_\mathrm a\over R}\left({1\over T_2} – {1\over T_1}\right)\right]} = 2 $$


Or simply:


$$ {k_2\over k_1} = \exp{\!\left({-E_\mathrm a\over R} \cdot \Delta{1\over T} \right)} = 2 $$


So:



$$ \exp{\!\left({-E_\mathrm a\over R} \cdot \Delta{1\over T} \right)} = 2 $$


This might be the part where I messed up -------------------------


$\Delta{1\over T}$ can be set in terms of $\Delta T$:


$$ \Delta{1\over T} = \left({1\over T_2}-{1\over T_1}\right) = \left({T_1\over T_1T_2}-{T_2\over T_1T_2}\right) = \left({T_1-T_2\over T_1T_2}\right) = \left({-\Delta T\over T_1T_2}\right) $$


Since Arrhenius' equation above holds true for $\Delta T = 10$ ...


And since $\Delta{1\over T}$ can be expressed as $-\Delta T \over T_1T_2$ ...


Then, the rate constant ($k$) will double when:


$$ \Delta{1\over T} = {-10\over T_1T_2} $$


Substituting into Arrhenius' equation:


$$ \exp{\!\left({-E_\mathrm a\over R}\cdot{-10\over T_1T_2}\right)} = 2 $$



Simplifying:


$$ \begin{align} \exp{\left({10E_\mathrm a\over RT_1T_2}\right)} &= 2 \\ {10E_\mathrm a\over RT_1T_2} &= \ln{2} \\ {1\over T_1 T_2} &= {R\cdot\ln{2}\over 10E_\mathrm a} \\ T_1 T_2 &= {10E_\mathrm a\over R\cdot\ln{2}} \end{align} $$


From $T_2 - T_1 = 10$ we can solve for $T_2$ as $T_2 = T_1 + 10$. Substituting above:


$$ \begin{align} T_1 (T_1 + 10) &= {10E_\mathrm a\over R\cdot\ln{2}} \\ T_1^2 + 10T_1 - {10E_\mathrm a\over R\cdot\ln{2}} &= 0 \end{align} $$


For $E_\mathrm a = 50\,000$:


$$ T_1^2 + 10T_1 - {500\,000\over R\cdot\ln{2}} = 0 $$


Solving the quadratic equation:


$$ \begin{align} T_1 &= 290~\mathrm K \\ T_2 &= 300~\mathrm K \\ \Delta T &= 10~\mathrm K \end{align} $$


I don't think this proof is correct because substituting any value for activation energy ($E_\mathrm a$) onto the quadratic equation will produce different values for $T_1$, but that doesn't tell me anything.


What did I do wrong? Can this be proved any other way?




Answer



Your method and your mathematics seem perfectly fine, and your calculated result is correct. You are also quite correct that the result will change depending on the value of $E_\mathrm a$ that you choose.


The problem you're running into is the assumption that the stated rule of thumb holds exactly, regardless of temperature. It doesn't.




I would set up the problem as follows. Consider the ratio $\rho$ between the reaction occurring at some Kelvin temperature $T$, and at $T+10$:


$$ \rho = {e^{-E_\mathrm a\over R\,\left(T+10\right)}\over e^{-E_\mathrm a\over RT}} = e^{{E_\mathrm a\over R}\left({1\over T} - {1\over T+10}\right)} = e^{{E_\mathrm a\over R}\cdot {10\over{T^2+10T}}} $$


Plotting $\rho$ as a function of $T$ for $E_\mathrm a = 50~\mathrm{kJ\over mol}$, it becomes immediately clear that the rule of thumb does not hold over a very wide temperature range:


Rate ratio versus temp


In fact, it only holds strictly for one specific temperature, which is why your math led you to a single temperature as your answer. By my calculations, using a value of $8.3144598~\mathrm{J\over mol\, K}$ for $R$, that temperature is $289.56~K$, which is equal to your $T_1=290~K$ to within three significant figures.


The gray box in the figure marks where the rule holds to within $20\%$ – that is, where $\rho$ falls between $1.6$ and $2.4$. This corresponds to a temperature range of $257~\mathrm K$ to $353~\mathrm K$.



grammar - Meaning of 今日も一日?




仕事を終えた労働者が、ダンジョンから無事戻ってきた冒険者達が、今日も一日の締めくくりとばかりに酒盛りに耽っている。



This is the first time I have come across this. What exactly does it mean and how would I use it? I've seen it in other sentences too like:



今日も一日頑張りましょう!



Thanks!



Answer



We have two very different 「今日{きょう}も一日{いちにち}」's here.




「今日も一日の締{し}めくくりとばかりに酒盛{さかも}りに耽{ふけ}っている。」



=



「今日も、一日の締{し}めくくりとばかりに酒盛{さかも}りに耽{ふけ}っている。」



≒



「一日の締めくくりとばかりに、今日も酒盛りに耽っている。」




Here, 「今日も ("today also")」 and 「一日 (the "work" day)」 function separately and independently from each other. Grammatically, it is not the same 「今日も一日」 that we use very often as a set phrase.


"Today, too, (they are) indulged in a drinking party as if it were the closing ceremony of the day."


Moving on...


The insanely common set phrase that I am talking about is the "other" 「今日も一日」 seen below.



「今日も一日頑張{がんば}りましょう!」



Here, 「今日も一日」 means "today as usual" or even just "as always". It works adverbially.


"Let us work hard (today) as usual!"



Tuesday, September 24, 2019

halacha - What degree of punishment is assigned to one who wants to commit a sin, but is only stopped by the lack of an opportunity?



For instance, if one thought of murdering a certain someone, but the only thing stopping him was the lack of an opportunity, would he be liable to a punishment equal to that of a murderer, or something lesser? Is there no punishment at all?


Is there a difference between an individual who would commit the sin of his thoughts versus one who wouldn't?


This question came to mind after the subject of freedom of choice came up on Shabbat at the synagogue. If someone were to wish, like Hitler, that they could wipe out all the Jews, but the only thing stopping them is a lack of opportunity, would their punishment be equal to his (whatever it is)?




animals - Why are there no fish korbanot?



Land animals, birds, wheat and fruit offerings all feature on the list of offerings that Bnei Israel bring for Hashem.


Is there anyone that discusses why there are no fish korbanot?



Answer



The Midrash Tanchuma (Vayikra 1:8) asks your question:



ולמה קריבין קרבן מן העוף ומן הכבשים ומן הצאן ומן העזים ולא מן הדגים, שנאמר, [ו] אם מן העוף עולה קרבנו, אלא בשביל שהם בשר ודם כמו האדם ויוצאין מבטן אמן כמו האדם, מכפרים על האדם. אבל הדגים, ביצים הם ויוצאין מהן וחיין.


And why do we offer up sacrifices from birds, sheep and goats but not from fish?


Because they (animals and birds) resemble man as they are born from the stomach of their mother like man. Thus, they atone for man. Fish, however, are eggs, that they emerge from and live.



I do have a pshat as to what this means (obviously birds come from eggs, too), but I'll have to add this in later..



grammar - Understanding "よりを戻す" and "止めておこう"



I don't think us getting together tonight is such a good idea.


やっぱり今夜、よりを戻すのは止めておこう。




I would like to understand this sentence better, specifically the (idiomatic?) expression, "よりを戻す." I will parse the parts I am not sure of below to see if I grasp it correctly:


"やっぱり" "after all."


"よりを戻す" is an idiom(?) meaning "get back together."


"止めておこう" "Should let pass/should let the matter drop/let's quit"


If these are acceptable, how does "よりを戻す" express "get back together"?


And does the おこう in "止めておこう" derive from 置く?



Answer



As you correctly understood, よりを戻す is an idiom meaning for a broken couple to get back together.


[縒]{よ}る means “to twist threads together to make a thicker string.” [縒]{よ}りを戻す literally means to undo this process and turn a string into several threads apart. This may sound like the opposite of getting back together (certainly it does sound like the opposite to me), but I guess that the analogy here is that “twisting” refers to the conflict between a couple, and removing the twist corresponds to getting back together.


おこう in [止]{や}めておこう is etymologically derived from 置く (to put), but here …ておく means “to do … for now.” In this context, よりを戻すのをやめておく means to avoid getting back together for now.



digital communications - Understanding the Matched Filter

I have a question about matched filtering. Does the matched filter maximise the SNR at the moment of decision only? As far as I understand, ...