The cache layer will serialize requests whose responses may potentially be used for each other, at least until the first request gets headers (Then the cache layer will merge the requests, if it can, depending on caching response headers).
If NIKs are enabled at the cache layer, requests with transient NIKs bypass the cache (even if the NIKs are the same), so there's no problem.
If NIKs are disabled at the cache layer (As is the case in AndroidWebView and cast, and may be the case if we're running eperiments that disable cache partitioning, or for 3P embedders), then the responses to the requests can potentially be used to service each other, so there will be blocking.
If this is a problem, I suggest just using the LOAD_BYPASS_CACHE load flag, which will always bypass the cache, and make the issue moot.