This is my first post on StackExchange, and I hope it is helpful. COOLSerdash gave a very complete answer already which I mostly agree with, but I will try to add a different perspective on the problem.
As you stated, $X_{k} \sim Binomial(n=100,p=\frac{1}{5}) \equiv 100 \times Bernoulli(\frac{1}{5})$
$\text{Cov}(X_5,X_k) = \mathbb{E}[(X_5-\mathbb{E}[X_5])(X_k-\mathbb{E}[X_k])]$
This leads to the expression $\mathbb{E}[X_5X_k]-\mathbb{E}[X_5]\mathbb{E}[X_k] = \mathbb{E}[X_5X_k]-100\times(\mathbb{E}(Bernoulli(\frac{1}{5}))$
$= \mathbb{E}[X_5X_k]-100\times(\frac{1}{25})=\mathbb{E}[X_5X_k]-4$.
Therefore, we have three conditions:
$k = 5 ; Cov(X_5,X_5) = Var(X_5) = Var(X_k) = 16$
$k \neq 3,7; Cov(X_5,X_k) = \mathbb{E}[X_5X_k]-4 = 0$
Consider the events $A := ${box $5$ gets a ball} , $B$ {box $k$ gets a ball} $\neq 3,7$, then $ \mathbb{P}(A,B) = \mathbb{P}(A)\mathbb{P}(B)$ due to independence.
$\therefore \mathbb{E}[X_5X_k]=100\times \mathbb{E}[A]\mathbb{E}[B]=100\times(\frac{1}{5}\times \frac{1}{5}) = 4$
$k = 3,7; Cov(X_5,X_k) = \mathbb{E}[X_5X_k]-4 = 6$ (as COOLSerdash stated)
With the defined events $A$ and $B$ for $k = 3,7$, $ \mathbb{P}(A,B) = \frac{1}{10}$ since the probability $A \cap B$ is the probability that box 4 (if $k=3$) or box 6 (if $k=7$) gets a ball.
Hope this helps!