Thursday, May 24, 2018

organic chemistry - Use of combinations to determine number of isomers


Our teacher asked us how many geometrical isomers are possible with the formula $\ce{c2ClBrIf}$. I answered with the logic $^4C_2=6$ and it turned out to be correct.


Is the use of combinations this way generally helpful in determining the number of possible isomers? For example, if I have a rigid molecule with three carbon atoms and six substituents (perhaps a cyclopropane), is the correct number of possible isomers 20?


$$^6 C_3 =\dfrac{6!}{(6-3)!\cdot 3!}= 20$$



Answer



For the following I've numbered the positions on ethylene where the four halogen atoms could go. (The Carbon-Carbon double bond doesn't "spin.") It doesn't matter which halogen goes to 1, so let's make it Fluorine. If Fluorine were in any other position then you could flip or rotate the molecule to get Fluorine to position 1. Now there are three choices left for position 2, which leaves 2 choices for position 3. So the number of possible isomers is:


$3 \times 2 = 6$


Note that if you just willy nilly drew molecules then you could draw 4! or 24 permutations. However when you rotate and flip the molecules, then only 6 unique molecules exist.


enter image description here


image processing - Difference between SNR and PSNR


I understood that SNR is the ratio of signal power to the noise power. In terms of images, how the original image is affected by the added noise. In PSNR, we take the square of the peak value in the image (in case of an 8 bit image, the peak value is 255) and divide it by the mean square error. The SNR and PSNR are used to measure the quality of an image after the reconstruction. I understand that higher the SNR or PSNR, the reconstruction is good. What I don't understand is how SNR and PSNR differs in terms of their conclusion about the reconstructed image.



  • What the PSNR of an image concludes that the SNR of the same image can't conclude ?

  • Simply how the conclusion of PSNR differs from the conclusion of SNR?




Answer



Let's start with the mathematical definitions.


Discrete signal power is defined as $$P_s = \sum_{-\infty}^{\infty}s^2[n] = \left|s[n]\right|^2.$$


We can apply this notion to noise $w$ on top of some signal to calculate $P_w$ in the same way. The signal to noise ratio (SNR) is then simply $$P_{SNR}=\frac{P_s}{P_w}$$


If we've received a noise corrupted signal $x[n] = s[n]+w[n]$ then we compute the SNR as follows


$$P_{SNR}=\frac{P_s}{P_w} = \frac{P_s}{\left|x[n]-s[n]\right|^2}.$$


Here $\left|x[n]-s[n]\right|^2$ is simply the squared error between original and corrupted signals. Note that if we scaled the definition of power by the number of points in the signal, this would have been the mean squared error (MSE) but since we're dealing with ratios of powers, the result stays the same.


Let us now interpret this result. This is the ratio of the power of signal to the power of noise. Power is in some sense the squared norm of your signal. It shows how much squared deviation you have from zero on average.


You should also note that we can extend this notion to images by simply summing twice of rows and columns of your image vector, or simply stretching your entire image into a single vector of pixels and apply the one-dimensional definition. You can see that no spacial information is encoded into the definition of power.



Now let's look at peak signal to noise ratio. This definition is


$$P_{PSNR}=\frac{\text{max}(s^2[n])}{\text{MSE}}.$$


If you stare at this for long enough you will realize that this definition is really the same as that of $P_{SNR}$ except that the numerator of the ratio is now the maximum squared intensity of the signal, not the average one. This makes this criterion less strict. You can see that $P_{PSNR} \ge P_{SNR}$ and that they will only be equal to each other if your original clean signal is constant everywhere, and with maximum amplitude. Notice that although the variance of a constant signal is null, its power is not; the level of such constant signal does make a difference in SNR but not in PSNR.


Now, why does this definition make sense? It makes sense because the case of SNR we're looking at how strong the signal is and to how strong the noise is. We assume that there are no special circumstances. In fact, this definition is adapted directly from the physical definition of electrical power. In case of PSNR, we're interested in signal peak because we can be interested in things like the bandwidth of the signal, or number of bits we need to represent it. This is much more content-specific than pure SNR and can find many reasonable applications, image compression being on of them. Here we're saying that what matters is how well high-intensity regions of the image come through the noise, and we're paying much less attention to how we're performing under low intensity.


gentiles - Are sex change operations prohibited for non-Jews?


In very specific situations some halachic decisors have permitted sex change operations, such as for infants born with some types of genital anomalies. However, the consensus seems to be that they are generally forbidden, at least for Jews. This is because they involve various halachic prohibitions, such as the prohibition on sterilization.


Are sex change operations prohibited to non-Jews as well? Why or why not?


Sources:






parshanut torah comment - When did G-d create darkness?


Bereshit 1:5 says:



וַיִּקְרָ֨א אֱלֹהִ֤ים ׀ לָאוֹר֙ י֔וֹם וְלַחֹ֖שֶׁךְ קָ֣רָא לָ֑יְלָה וַֽיְהִי־עֶ֥רֶב וַֽיְהִי־בֹ֖קֶר י֥וֹם אֶחָֽד׃ (פ
And God called the light Day, and the darkness He called Night. And there was evening and there was morning, one day.




The Haamek Davar commentary explains this pasuk as follows:



And to the darkness, He called night: The Sages, of blessed memory, explained in the beginning of Tractate Pesachim, that the Holy One, blessed be He, called to darkness and appointed it over the night. [By this,] our Rabbis taught us that we should not say that darkness is only the absence of light, like when - in the middle of the day - we close the windows, it becomes dark. For, if so, it would not be a creation. But in truth, darkness is a creation, on its own as well, as it is written (Isaiah 45:7), "and created the darkness." And it is great distortion to say that darkness is only the absence of light. But rather, God makes both of them, just as He concerns Himself over holiness and impurity.



This explanation states that darkness is a creation on it's own rather than just the absence of light, and it even quotes Isaiah as direct evidence. However, the creation of light is explicitly narrated in Bereshit 1:3 :



וַיֹּ֥אמֶר אֱלֹהִ֖ים יְהִ֣י א֑וֹר וַֽיְהִי־אֽוֹר׃



and it's separation from darkness is recounted in Bereshit 1:4 :




וַיַּ֧רְא אֱלֹהִ֛ים אֶת־הָא֖וֹר כִּי־ט֑וֹב וַיַּבְדֵּ֣ל אֱלֹהִ֔ים בֵּ֥ין הָא֖וֹר וּבֵ֥ין הַחֹֽשֶׁךְ׃



But darkness (as well as the deep/תְה֑וֹם) is named on Bereshit 1:2 without a narration of its creation earlier:



וְהָאָ֗רֶץ הָיְתָ֥ה תֹ֙הוּ֙ וָבֹ֔הוּ וְחֹ֖שֶׁךְ עַל־פְּנֵ֣י תְה֑וֹם וְר֣וּחַ אֱלֹהִ֔ים מְרַחֶ֖פֶת עַל־פְּנֵ֥י הַמָּֽיִם׃



I understand that the account of Creation of Bereshit contains really deep meanings and may not be as literal as I may be taking it according to the sages' interpretations. However, I believe it is a valid question to ask: When did G-d create darkness?


I suspect darkness (and the deep) may've been in some way part of the creation of the heavens and the earth in Bereshit 1:1, but this is just a thought.




Edit:



The answers I've received are wonderful and really well researched, however I will not be choosing one as the correct answer for the following reason: Menachem's answer explains the perspective of the Ohr HaChaim and the Talmud, which states that darkness was created in the first day, with a solid reasoning. While Mevaqesh's answer argues that darkness is in fact just the absence of light (and not a creation), and he justifies this point by quoting many different rabbinical authorities from different backgrounds and centuries who all agree with this interpretation.


I don't feel I'm entitled to choose which answer is the most correct based on my subjective opinion and I encourage the readers to check both of this great answers to get an understanding of both conflicting yet fascinating interpretations.




parshanut torah comment - Different words for "desire"


In the (second presentation of the) tenth commandment (Deut 5:17), why does the Torah use two different words in Hebrew (תחמד and תתאוה) that mean almost the same thing is English ("covet" or "desire"). I can find no explanation in Rashi. What is the difference between those words?



Answer



There are at least two opinions that differentiate halachically between the two terms:


The Rambam in M.T. (Gzeilah 1:9-10) and Shulchan Aruch (C.M. 359) hold that לא תתאוה refers to plotting to acquire the coveted item, while לא תחמד refers to actually pressuring the owner into giving it to him.


The Sefer Hachinuch (417) (and perhaps the Rambam in Sefer Hamitzvos L.S. 266) hold that לא תתאוה refers even to mere desire.



It is important to note that (in light of the above ruling of the Shulchan Aruch), contrary to popular belief, it is not forbidden to feel envious of someone else's possessions, as long as you don't begin to think about how you can get them from him.


organic chemistry - Is the ethyl cation really more stable than benzylic and allylic carbocations?



enter image description here Source: Concepts of Organic chemistry by O.P. Tandon, page no. 235



My book appears to state that the ethyl cation (a primary carbocation) is more stable than both allyl and benzyl carbocations.


I knew that cation stability depends on the following factors: resonance > hyperconjugation > +inductive effect.


Can someone please clarify whether the ranking shown above is true?




Why don't metals form covalent bonds in bulk metal?


I really don't understand why metals form metallic bonds. I mean, it makes no sense. It would make much more sense for them to form covalent bonds with themselves and have a 'pseudo-full' outer shell. How does freeing off electrons make them any more stable?



Answer



This is due to the low ionization energies of the metals. It's easier for them to release few electrons from the outer shell to obtain a noble gas configuration rather than consuming several ones. However, the difference between an ionic and a polar covalent bond is always fringe.


Again, it's not true that metals don't form covalent bonds at all. I guess you never heard of quadruple bond or δ-bond. There are several examples such as $\ce{K2[Re2Cl8]·2H2O}$ and Chromium(II) acetate hydrate.


periodic trends - Comparing radii in lithium, beryllium, magnesium, aluminium and sodium ions

Apparently the of last four, $\ce{Mg^2+}$ is closest in radius to $\ce{Li+}$. Is this true, and if so, why would a whole larger shell ($\ce{...